Catalyst System and Process for Olefin Polymerization

ABSTRACT

The present application relates to a new catalyst system for the polymerization of olefins, comprising a new ionic activator having the formula: [R 1 R 2 R 3 AH] +  [Y] − , wherein [Y] −  is a non-coordinating anion (NCA), A is nitrogen or phosphorus, R 1  and R 2  are hydrocarbyl groups or heteroatom-containing hydrocarbyl groups and together form a first, 3- to 10-membered non-aromatic ring with A, wherein any number of adjacent ring members may optionally be members of at least one second, aromatic or aliphatic ring or aliphatic and/or aromatic ring system of two or more rings, wherein said at least one second ring or ring system is fused to said first ring, and wherein any atom of the first and/or at least one second ring or ring system is a carbon atom or a heteroatom and may be substituted independently by one or more substituents selected from the group consisting of a hydrogen atom, halogen atom, C 1  to C 10  alkyl, C 5  to C 15  aryl, C 6  to C 25  arylalkyl, and C 6  to C 25  alkylaryl, and R 3  is a hydrogen atom or C 1  to C 10  alkyl, or R 3  is a C 1  to C 10  alkylene group that connects to said first ring and/or to said at least one second ring or ring system. The present application also relates to a process for the polymerization of olefins, preferably propylene, using this and other catalyst systems, as well as to polymers made by said process.

FIELD OF THE INVENTION

This invention relates to a new catalyst system that includes atransition metal compound and an activator, the activator comprising anon-coordinating anion and a cyclic cation. The invention also relatesto processes for polymerizing olefins using such and related catalystsystems. The invention further relates to the polymers producedtherefrom.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems, including catalystactivators that increase the polymerization activity of the catalyst andallow the production of polymers having specific properties, such ashigh melting point and high molecular weight.

Catalysts for olefin polymerization are often based on metallocenes ascatalyst precursors, which are activated either with the help of analumoxane, or with an activator containing a non-coordinating anion.

EP-A-0 277 004 is one of the first documents disclosing polymerizationcatalysts comprising a bis-Cp metallocene compound that is activated byreaction with a secondary, ionic component comprising a non-coordinatinganion (NCA) and a counter-cation. The NCA is, on the one hand, capableof stabilizing the active cationic catalyst species, but on the otherhand only weakly coordinates to the metal center and thus can bedisplaced by a monomer to be incorporated into the polymer chain. Theactivators disclosed are ion pairs of an ammonium or phosphonium cationand a borate anion as the NCA. The cations disclosed are alkyl and/oraryl ammonium or phosphonium species. EP-A-0 277 004 states that theconjugate base of the activator cation should be a neutral componentwhich stays in solution and which preferably does not coordinate to themetal cation. Therefore, it is suggested to use relatively bulkyconjugate Lewis bases to avoid coordination to and thus interfering withthe active catalyst.

WO 91/02012 discloses the polymerization of high Mw, narrow molecularweight distribution (MWD) polyethylene using a metallocene/activatorsystem, wherein the activator comprises an NCA and an ammonium cation.Cyclic, non-aromatic ammonium cations are not disclosed.

M. A. Giardello, M. S. Eisen, Ch. L. Stern and T. J. Marks in J. Am.Chem. Soc. 1995, 117, 12114-12129, report on the preparation of cationicpolymerization catalysts from metallocene compounds, using various typesof activators, including methylalumoxane (MAO) and NCA/cation pairs. Itis suggested that, although the main focus in activator choice is on theNCA, the choice of the amine in the activator cation may also beimportant, as certain amines could coordinate to the metallocene cationand thus diminish its catalytic activity. In accordance with thissuggestion is another finding also reported in this article, which isthat the presence of an exogenous amine base significantly depresses theMw of the polymer product as well as the polymerization activity.

EP-A-0 630 910 teaches the use of free Lewis bases to control theactivity of olefin polymerization catalysts. Lewis bases can, ifnecessary, terminate the catalytic reaction completely. However, thetermination is reversible upon addition of alumoxane. The systemdisclosed thus comprises a metallocene compound, a Lewis base and analumoxane. EP-A-0 630 910 indicates that the metallocene cation—Lewisbase complex is inactive for olefin polymerization because the olefin isunable to compete with the Lewis base for the coordination site at themetal. The Lewis bases used are, among others, amines, ethers orphosphines.

Despite the earlier teachings in the art as reported above, severalauthors and patent applications teach the separate addition of an aminebase to the system comprising the metallocene compound, the cation/NCAactivator and, optionally, an organoaluminum compound. See for exampleU.S. Pat. No. 5,817,590, and E. A. Sanginov, A. N. Panin, S. L.Saratovskikh, N. M. Bravaya, in Polymer Science, Series A (2006), 48(2),99-106.

U.S. Pat. No. 5,416,177 discloses the use of metallocene compounds incombination with activators comprising tris(pentafluorophenyl)borane andat least one complexing compound, such as water, alcohols, mercaptans,silanols, and oximes, for the polymerization of olefins, in particular1-hexene. Similar catalyst systems are disclosed in WO 2005/016980.

WO 01/62764, WO 01/68718 and WO 2004/005360 disclose co-catalysts foruse in olefin polymerization, wherein the co-catalysts comprise a cationderived from an aromatic, nitrogen-containing Lewis base, such aspyrrole, imidazole or indole, and NCAs, particularly borates.

WO 01/48035 relates to catalyst systems comprising an organometalliccompound (preferably a metallocene), a Lewis base, a support, and anactivator. The activator is an ion pair, the anion of which is a borate,such as tetrakis(pentafluorophenyl)borate. The cation is an ammoniumcation, such as a trialkylammonium. No cations are disclosed wherein thenitrogen atom is part of a non-aromatic ring, or where the three alkylgroups are identical.

WO 03/035708 seeks to provide a cocatalyst component for use incombination with olefin polymerization catalyst precursors, particularlymetallocenes that result in highly active polymerization catalysts withgood storage stability. The cocatalysts disclosed are composed of anammonium cation and a NCA and are supported on a fine particle carrier.The substituents used in the ammonium cation are selected from hydrogen,alkyl and arylalkyl. The NCA is of a similar type as disclosed e.g. inU.S. Pat. No. 5,416,177 discussed above. It is also said that thesubstituents may form a ring with each other, but no specific examplesor suggestions of such compound are made.

There is still a need in the art for new and improved catalyst systemshaving good activity for the polymerization of olefins, in order toachieve specific polymer properties, such as high melting point, highmolecular weights or to increase conversion without deteriorating theresulting polymer's properties. Also, in propylene polymerizationincreased propylene conversion often goes along with a decrease inmolecular weight.

It is therefore an object of the present invention to provide a processand a catalyst system for use in a process for the polymerization ofolefins, especially propylene, wherein the resulting polymers have ahigh molecular weight and/or a high melting point. Ideally, suchcatalyst system should also exhibit high catalytic activity under(propylene) polymerization conditions.

It is also an object of the present invention to provide a process and acatalyst system for use in a process for polymerizing olefins,especially propylene, which process and catalyst system allow raisingolefin conversion rates, without substantially lowering the molecularweight of the resulting polymer, thus making commercial polymerizationprocesses more efficient.

SUMMARY OF THE INVENTION

This invention relates to a catalyst system comprising a transitionmetal compound and an activator, the activator having the formula (1):

[R¹R²R³AH]⁺ [Y]⁻,   (1)

wherein [Y]⁻ is a non-coordinating anion (NCA),A is nitrogen or phosphorus,R¹ and R² are hydrocarbyl groups or heteroatom-containing hydrocarbylgroups and together form a first, 3- to 10-membered non-aromatic ringwith A, wherein any number of adjacent ring members may optionally bemembers of at least one second, aromatic or aliphatic ring or aliphaticand/or aromatic ring system of two or more rings, wherein said at leastone second ring or ring system is fused to said first ring, and whereinany atom of the first and/or at least one second ring or ring system isa carbon atom or a heteroatom and may be substituted independently byone or more substituents selected from the group consisting of ahydrogen atom, halogen atom, C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅arylalkyl, and C₆ to C₂₅ alkylaryl, and R³ is a hydrogen atom or C₁ toC₁₀ alkyl, or R³ is a C₁ to C₁₀ alkylene group that connects to saidfirst ring and/or to said at least one second ring or ring system.

The present invention also relates to a process for polymerizing one ormore olefins, comprising contacting under polymerization conditions oneor more olefin monomers, preferably propylene, with a catalyst systemcomprising a transition metal compound and an activator of the formula(1) as defined above.

Equally, the present invention relates to the use of a compound offormula (1) as defined above in a catalyst system for the polymerizationof one or more olefins, preferably propylene, as activator of atransition metal compound.

The invention furthermore relates to a process for polymerizing one ormore olefins, comprising contacting under polymerization conditions oneor more olefin monomers with a catalyst system comprising a transitionmetal compound and an activator of the following formula (2):

[R_(n)AH]⁺ [Y]⁻,   (2)

wherein [Y]⁻ is a non-coordinating anion (NCA),A is nitrogen, phosphorus or oxygen,n is 3 if A is nitrogen or phosphorus, and n is 2 if A is oxygen,and the groups R are identical or different and are a C₁ to C₃ alkylgroup, wherein the weight average molecular weight (Mw) of the polymerformed increases or at least does not substantially decrease withincreasing monomer conversion at a given reaction temperature.

The present invention also relates to a polymer obtainable by any of theabove-described processes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows weight average molecular weight (g/mol) versus propyleneconversion of the resulting polymer in a propylene polymerizationreaction conducted batch-wise at a temperature of 120° C. withrac-dimethylsilylbis(indenyl) hafnium dimethyl and different cation/NCAactivators, both according to the present invention as well ascomparative, see Example 1.

FIG. 2 a shows Mw versus reaction temperature (° C.) of the resultingpolymer in a propylene polymerization reaction withrac-dimethylsilylbis(indenyl) hafnium dimethyl,tetrakis(pentafluorophenyl)borate andtetrakis(heptafluoronaphthyl)borate and two different counter-cations,trimethylammonium (according to the present invention) anddimethylanilinium (comparative), see Example 2.

FIG. 2 b shows melting point (° C.) of the resulting polymer versusreaction temperature (° C.) in a propylene polymerization reaction withrac-dimethylsilylbis(indenyl) hafnium dimethyl,tetrakis(pentafluorophenyl)borate andtetrakis(heptafluoronaphthyl)borate and two different counter-cations,trimethylammonium (according to the present invention) anddimethylanilinium (comparative), see also Example 2.

FIG. 3 a shows the viscosity of the resulting polymer measured at 190°C. versus reaction temperature (° C.) in a propylene polymerizationreaction with rac-dimethylsilylbis(indenyl) zirconium dimethyl,tetrakis(heptafluoronaphthyl)borate and two different counter-cations,trimethylammonium (according to the present invention) anddimethylanilinium (comparative), see also Example 3.

FIG. 3 b shows melting point (° C.) of the resulting polymer versusreaction temperature (° C.) in a propylene polymerization reaction withrac-dimethylsilylbis(indenyl) zirconium dimethyl,tetrakis(heptafluoronaphthyl)borate and two different counter-cations,trimethylammonium (according to the present invention) anddimethylanilinium (comparative), see also Example 3.

In FIGS. 2 a, 2 b, 3 a, and 3 b “Me3” is trimethyl.

Definitions

For the purposes of this invention, a “catalyst system” is a combinationof different components that, taken together, provide the activecatalyst. A catalyst system of the present invention therefore comprisesat least a transition metal compound (also referred to herein as“precatalyst” or “catalyst precursor”, these two terms being identicalin meaning and being used interchangeably) and an activator. Anactivator is also sometimes referred to as a “co-catalyst” (again, thesethree terms are all identical in meaning and are used interchangeably).The activator activates the transition metal compound and converts itinto its catalytically active form. For example, an activator converts aneutral metallocene compound into its cationic form, which is thecatalytically active species. When the term “catalyst system” is used todescribe a catalyst/activator pair before activation, it refers to theunactivated catalyst (i.e., the precatalyst) together with an activator.When this term is used to describe a catalyst/activator pair afteractivation, it refers to the activated catalyst and the charge-balancinganion derived from the activator or other charge-balancing moiety. Theactual catalyst may be generated only shortly before or while it isbeing contacted with the reactants (in the case of a polymerizationreaction the monomers). Usually, catalysts are commercially offered andshipped in the form of neutral compounds (e.g., the neutral metallocenecompound). In the scientific and commercial literature the term“catalyst” is sometimes used to refer to the non-activated (i.e.,neutral and stable) metallocene, which still has to be converted to itsrespective charged form in order to react with the monomers to producepolymer. The catalyst system may be in the form of an actual compositionprepared from the transition metal compound and the activator (thusresulting in an activated cationic catalyst, a counter-anion andadditional components originating from the activator, such as a freeLewis base), or in the form of a “kit” containing, separately, thetransition metal compound and the activator to be combined wheneverneeded. Such “kit” may also contain, separately or combined with eitherthe transition metal compound or the activator or both, additionalcomponents that are conventionally used in polymerization reactions,such as scavenging compounds etc. Finally, the components of thecatalyst system may, either separately or jointly, be supported on asolid support, such as alumina or silica.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities (poisons that would otherwisereact with the catalyst and deactivate it). Some scavengers may also actas activators, and they may also be referred to as co-activators. Aco-activator may be used in conjunction with an activator in order toform an active catalyst.

For the purposes of this invention, it is understood that whenever apolymer is referred to as “comprising” an olefin or other monomer, theolefin present in the polymer is the polymerized form of the olefin orother monomer, respectively. Mw refers to the weight average molecularweight, Mn to the number average molecular weight and Mz to theZ-average molecular weight. All molecular weights are g/mol unlessotherwise noted. A “reactor” as referred to herein is understood to beany container(s) in which a chemical reaction occurs. As used herein, Meis methyl, Et is ethyl, t-Bu and ^(t)Bu are tertiary butyl, n-Bu and nBuare n-butyl, iPr and ^(i)Pr are isopropyl, Cy is cyclohexyl, THF (alsoreferred to as thf) is tetrahydrofuran, Bn is benzyl, and Ph is phenyl.

As used herein, the numbering scheme for the Periodic Table Groups is aspublished in Chemical and Engineering News, 63(5), 27 (1985).

The terms “radical”, “group”, and “substituent” are used interchangeablyherein and indicate a group that is bound to a certain atom as indicatedherein. A “substituted” group is one where a hydrogen has been replacedby a hydrocarbyl, a heteroatom or a heteroatom containing group. Forexample, methyl cyclopentadiene is a cyclopentadiene substituted with amethyl group.

The term “hydrocarbyl” is used herein to refer to anyhydrocarbon-derived substituent or group and thus is understood toinclude, without limitation, linear, branched or cyclic alkyl, alkylene,alkene, alkine, as well as aryl groups. Any of these groups may besubstituted or unsubstituted.

The term “alkyl” is used herein to refer to an aliphatic, branched orlinear, non-cyclic or cyclic substituent typically with a certain numberof carbon atoms as individually specified. Unless specified otherwiseherein, “alkyl” specifically includes aliphatic groups having from 1 to20, preferably from 1 to 10, and more preferably from 1 to 5 carbonatoms, and specifically methyl, ethyl, propyl, n-propyl, isopropyl,butyl, n-butyl, isobutyl, pentyl, n-pentyl, isopentyl, cyclopentyl,hexyl, n-hexyl, isohexyl, cyclohexyl, heptyl, n-heptyl, isohexyl,cycloheptyl, octyl, n-octyl, isooctyl, cyclooctyl, nonyl, n-nonyl,isononyl, decyl, n-decyl, iso-decyl and the like. The same definitionapplies for the alkyl in an alkoxy substituent.

The term “aryl” is used herein to refer to an aromatic substituent,which may be a single aromatic ring or multiple aromatic rings, whichare fused together, covalently linked, or linked to a common group suchas a methylene or ethylene moiety. The common linking group may also bea carbonyl as in benzophenone or oxygen as in diphenylether. Thearomatic ring(s) may include phenyl, naphthyl, fluorenyl, indenyl,biphenyl, diphenylether, tolyl, cumyl, xylyl, and benzophenone, amongothers. Unless specified otherwise herein, the term “aryl” specificallyincludes those having from 5 to 30, preferably from 5 to 25 morepreferably from 5 to 20, and more preferably from 5 to 15 carbon atoms,alternately the aryl may have 6 to 15 carbon atoms or may have 5 or 6carbon atoms. “Substituted aryl” refers to aryl as just described inwhich one or more hydrogen atoms to any carbon are, independently ofeach other, replaced by one or more groups such as alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, alkylhalogen, such as hydroxyl-, phosphino-,alkoxy-, aryloxy-, amino-, thio- and both saturated and unsaturatedcyclic hydrocarbons which are fused to the aromatic ring(s), linkedcovalently or linked to a common group such as a methylene or ethylenemoiety. The linking group may also be a carbonyl such as in cyclohexylphenyl ketone. The term “aryl” also includes aromatic groups containingone or more heteroatoms, such as nitrogen, oxygen, phosphorus or sulfur.Non-limiting examples of such hetero-atom containing aromatic groups arefuranyl, thiophenyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl,benzofuranyl, pyrazinyl, pyrimidinyl, pyridazinyl, chinazolinyl,indolyl, carbazolyl, oxazolyl, thiazolyl, and the like.

The term “ring system” refers to any system or combination of aliphaticand/or aromatic rings that are fused to each other via shared ringmember atoms, that are covalently linked to each other or that arelinked via a common linking group, such as an alkylene group or ahetero-atom containing group such as carbonyl. One or more of thealiphatic and/or aromatic rings of the ring system may also contain oneor more heteroatoms, such as nitrogen, oxygen, phosphorus or sulfur. Anyof the aliphatic and/or aromatic rings of the ring system may besubstituted by one or more groups such as alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, alkylhalogen, such as hydroxyl-, phosphino-,alkoxy-, aryloxy-, amino-, thio- and both saturated and unsaturatedcyclic hydrocarbons. For the aromatic or aliphatic rings of the ringsystem, the above-provided definitions for “aryl” and “alkyl” regardingthe number of carbon atoms apply as well. A ring system in the contextof the present invention contains at least two rings. A “ring carbonatom” is a carbon atom that is part of a cyclic ring structure. By thisdefinition, a benzyl group has six ring carbon atoms andpara-methylstyrene also has six ring carbon atoms.

The term “amino” is used herein to refer to the group —NQ¹Q², where eachof Q¹ and Q² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

DETAILED DESCRIPTION

This invention relates to new catalyst systems comprising a transitionmetal compound and an activator of formula (1). In another aspect, thepresent invention also relates to a process of polymerizing one or moreolefin monomers using a catalyst system comprising a transition metalcompound and an activator of formula (1) or (2). The components of thecatalyst systems according to the present invention and used in thepolymerization process of the present invention are described in moredetail herein below.

Activators and Activation Methods for Catalyst Compounds

The transition metal compounds are activated to yield the catalyticallyactive, cationic transition metal compound having a vacant coordinationsite to which a monomer will coordinate and then be inserted into thegrowing polymer chain. In the process for polymerizing olefins accordingto the present invention, an activator of the following general formulae(1) or (2) is used to activate the transition metal compound:

Formula (1) is:

[R¹R²R³AH]⁺ [Y]⁻  (1)

wherein [Y]⁻ is a non-coordinating anion (NCA) as further illustratedbelow,A is nitrogen or phosphorus,R¹ and R² are hydrocarbyl groups or heteroatom-containing hydrocarbylgroups and together form a first, 3- to 10-membered non-aromatic ringwith A, wherein any number of adjacent ring members may optionally bemembers of at least one second, aromatic or aliphatic ring or aliphaticand/or aromatic ring system of two or more rings, wherein said at leastone second ring or ring system is fused to said first ring, and whereinany atom of the first and/or at least one second ring or ring system isa carbon atom or a heteroatom and may be substituted independently byone or more substituents selected from the group consisting of ahydrogen atom, halogen atom, C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅arylalkyl, and C₆ to C₂₅ alkylaryl, andR³ is a hydrogen atom or C₁ to C₁₀ alkyl, or R³ is a C₁ to C₁₀ alkylenegroup that connects to said first ring and/or to said at least onesecond ring or ring system.

Formula (2) is:

[R_(n)AH]⁺ [Y]⁻  (2)

wherein [Y]⁻ is a non-coordinating anion (NCA) as further illustratedbelow,A is nitrogen, phosphorus or oxygen,n is 3 if A is nitrogen or phosphorus, and n is 2 if A is oxygen,and the groups R are identical or different and are a C₁ to C₃ alkylgroup.

The present invention thus specifically relates to the new catalystsystem itself, comprising a transition metal compound and an activatorof the formula (1) shown above, to the use of an activator of saidformula (1) for activating a transition metal compound in a catalystsystem for polymerizing olefins, and to a process for polymerizingolefins the process comprising contacting under polymerizationconditions one or more olefins with a catalyst system comprising atransition metal compound and an activator of formula (1).

The present invention also relates to a process for polymerizing olefinsthe process comprising contacting under polymerization conditions one ormore olefins with a catalyst system comprising a transition metalcompound and an activator of formula (2) as shown above. In thisprocess, the weight average molecular weight of the polymer formedincreases with increasing monomer conversion at a given reactiontemperature.

Both the cation part of formulae (1) and (2) as well as the anion partthereof, which is an NCA, will be further illustrated below. Anycombinations of cations and NCAs disclosed herein are suitable to beused in the processes of the present invention and are thus incorporatedherein.

Activators—The Cations

The cation component of the activator of formulae (1) or (2) above isusually a protonated Lewis base capable of protonating a moiety, such asan alkyl or aryl, from the transition metal compound. Thus, upon releaseof a neutral leaving group (e.g. an alkane resulting from thecombination of a proton donated from the cationic component of theactivator and an alkyl substituent of the transition metal compound) atransition metal cation results, which is the catalytically activespecies.

In the polymerization process of the present invention an activator ofabove-depicted formula (2) may be used, wherein the cationic componenthas the formula [R_(n)AH]⁺, wherein:

A is nitrogen, phosphorus or oxygen,n is 3 if A is nitrogen or phosphorus, and n is 2 if A is oxygen,and the groups R are identical or different and are a C₁ to C₃ alkylgroup. [R_(n)AH]⁺ may thus be an ammonium, phosphonium or oxoniumcomponent, as A may be nitrogen, phosphorus or oxygen.

In one preferred embodiment of formula [R_(n)AH]⁺, A is nitrogen orphosphorus, and thus n is 3, and the groups R are identical. Morepreferably, n is 3, and the groups R are all identically methyl, ethylor propyl groups, more preferably [R_(n)AH]⁺ is trimethylammonium or-phosphonium, triethylammonium or -phosphonium, tri(iso-propyl)ammoniumor -phosphonium, tri(n-propyl)ammonium or -phosphonium.Trimethylammonium is particularly preferred. If [R_(n)AH]⁺ is an oxoniumcompound (with n being 2), it is preferably the oxonium derivative ofdimethyl ether, diethyl ether, tetrahydrofurane and dioxane.

In another embodiment, an activator of above-depicted formula (1) isused in the polymerization process of the present invention, thecationic component of which has the formula [R¹R²R³AH]⁺, wherein A isnitrogen or phosphorus, R¹ and R² are hydrocarbyl groups orheteroatom-containing hydrocarbyl groups and together form a first, 3-to 10-membered non-aromatic ring with A, wherein any number, preferablytwo, three, four or five, more preferably two, of adjacent ring membersmay optionally be members of at least one second, aromatic or aliphaticring or aliphatic and/or aromatic ring system of two or more rings,wherein said at least one second ring or ring system is fused to saidfirst ring, and wherein any atom of the first and/or at least one secondring or ring system is a carbon atom or a heteroatom and mayindependently be substituted by one or more substituents selected fromthe group consisting of a hydrogen atom, halogen atom, C₁ to C₁₀ alkyl,preferably C₁ to C₅ alkyl, C₅ to C₁₅ aryl, preferably C₅ to C₁₀ aryl, C₆to C₂₅ arylalkyl, and C₆ to C₂₅ alkylaryl, and R³ is a hydrogen atom orC₁ to C₁₀ alkyl or a C₁ to C₁₀ alkylene group that connects to saidfirst ring and/or said at least second ring or ring system. Since R¹ andR² may also be heteroatom (e.g. nitrogen, phosphorus oroxygen)-containing hydrocarbyl groups, the 3- to 10-membered ring theyare forming with A and/or the at least one second ring or ring systemmay contain one or more additional heteroatoms (in addition to A), suchas nitrogen and/or oxygen. Nitrogen is a preferred additional heteroatomthat may be contained once or several times in said first ring and/orsaid at least one second ring or ring system. Any additional heteroatom,preferably nitrogen, may preferably be substituted independently by ahydrogen atom, or C₁ to C₅ alkyl.

One preferred embodiment of the cation in formula (1) is depicted in thefollowing formula (1)′:

In formula (1)′ R¹ and R² together are a —(CH₂)_(a)— (i.e., alkylene)group with a being 3, 4, 5 or 6, and A is preferably nitrogen, R³ is ahydrogen atom or C₁ to C₁₀ alkyl, or R³ is a C₁ to C₁₀ alkylene groupthat connects to the ring formed by A, R¹, and R². In a specificembodiment, R³ is an alkylene group with 1, 2 or 3 carbon atoms which isconnected to the ring formed by R¹, R² and A. R¹, R² and/or R³ may alsobe aza- or oxa-alkylene groups. R¹ and R² preferably form a 4-, 5-, 6-or 7-membered, non-aromatic ring with the nitrogen atom A.

Preferably, A in formula (1) or (1)′ is nitrogen, and R¹ and R² togetherare a —(CH₂)_(a)— group (also referred to as “alkylene” group) with abeing 3, 4, 5 or 6, or R¹ and R² may also be aza- or oxa-alkylene groupsas mentioned above. R¹ and R² preferably form a 4, 5-, 6- or 7-membered,non-aromatic ring with the nitrogen atom A. Non-limiting examples ofsuch ring are piperidinium, pyrrolidinium, piperazinium, indolinium,isoindolinium, imidazolidinium, morpholinium, pyrazolinium etc. Theadditional substituent at A, R³, is in any of these cases preferably C₁to C₅ alkyl, more preferably C₁ to C₄ alkyl, even more preferably C₁ toC₃ alkyl, and more preferably methyl or ethyl. R₃ may also be a C₁ to C₅alkylene group, preferably a C₁ to C₄ alkylene group, more preferably aC₁ to C₃ alkylene group and more preferably a —(CH₂)₃—, —(CH₂)₂ or —CH₂—group that connects to the first ring containing R¹, R² and A and/or theat least second ring or ring system fused to the first ring. Thus,[R¹R²R³AH]⁺ can also form a tricyclic structure, for example but notlimited to the following ones (which may be further substituted in oneor more positions by any substituents mentioned above and may containunsaturations, but are preferably not aromatic):

If additional heteroatoms are present in the first ring and/or the atleast one second ring or ring system, structures like the following,nonlimiting example (which, again, may be further substituted by one ormore substituents as mentioned above and may contain unsaturations, butare preferably not aromatic) may be used as the cation:

In another preferred embodiment the ring formed by R¹, R² and A is fusedto at least one other aliphatic or aromatic ring or ring system. Forexample, in the case that R¹, R² and A form a 5- or 6-membered aliphaticfirst ring with the heteroatom being phosphorus or nitrogen, one or more5- or 6-membered aromatic rings or ring systems may be fused to saidfirst ring via adjacent carbon atoms of the first ring.

In a preferred embodiment, [R¹R²R³AH]⁺ is N-methylpyrrolidinium,N-methylpiperidinium, N-methyldihydroindolinium orN-methyldihydroisoindolinium.

In another preferred embodiment the cation in formula (1) is depicted asone of the following four formulae (which are based upon formula (1) andare included when formula (1) is referred to herein.)

wherein each x is 0, 1 or 2, y is 3, 4, 5, 6, 7, 8, 9, or 10,(preferably 3, 4, 5, or 6), v is 1, 2, 3, 4, 5, 6, or 7 (preferably 0,1, 2 or 3), z is 1, 2, 3, 4, 5, 6, or 7 (preferably 0, 1, 2 or 3), andv+y+z=3, 4, 5, 6, 7, 8, 9, or 10 (preferably v+y+z=3, 4, 5 or 6), m is1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 (preferably 1, 2, 3, or 4), A isnitrogen or phosphorus (preferably nitrogen), R³ is a hydrogen atom orC₁ to C₁₀ alkyl, R* is a C₁ to C₁₀ alkyl, where any of the (CH_(x))groups may be substituted, independently, by one or more substituentsselected from the group consisting of a halogen atom, C₁ to C₁₀ alkyl,C₅ to C₁₅ aryl, C₆ to C₂₅ arylalkyl, and C₆ to C₂₅ alkylaryl. In anotherembodiment, at least one of the (CH_(x)) groups is replaced by aheteroatom, preferably nitrogen. In a preferred embodiment, the ringsdepicted in the formulae above are saturated or partially unsaturated,but are preferably not aromatic. Alternately, the ring containing(CH_(x))_(v), (CH_(x))_(y), and (CH_(x))_(z) is not aromatic, while thering containing (CH_(x))_(m) may or may not be aromatic.

The cationic component of the activator, when contacted with thetransition metal compound, will donate its proton and thus become aneutral Lewis base (donor) compound. The neutral Lewis bases originatingfrom the cationic components [R_(n)AH]⁺ and [R¹R²R³AH]⁺ describedhereinabove coordinate (but not irreversibly as they can still bedisplaced by the olefin monomer) to the transition metal. Withoutwishing to be bound by this theory, it is believed that a balancebetween strongly coordinating and non-coordinating Lewis bases has to befound in order to achieve the technical effects of the presentinvention, inter alia, to be able to homo- or co-polymerize olefins withhigh catalytic activity (productivity), and/or wherein at a givenreaction temperature the Mw of the polymer formed increases withincreasing monomer conversion and/or wherein the resulting polymers havehigh Mw and/or high melting points as described in more detail below.

The effect that the Mw of the polymer formed increases with monomerconversion at a given reaction temperature is illustrated in FIG. 1.With the catalyst systems comprising a transition metal compound and anactivator of formula (1) or (2), the slope of Mw versus monomerconversion is positive or at least even, whereas with comparativecatalyst systems comprising an activator that is not according toformula (1) or (2), usually a negative slope of Mw versus conversion isobserved.

The effect that with the present invention using activators of formula(1) or (2), preferably formula (1), in catalyst systems comprising atransition metal compound as described herein polyolefins, preferablypolypropylene, with higher Mw and at the same time higher melting pointare obtained than with comparative catalyst systems containingconventional activators, is illustrated in FIGS. 2 a and 2 b as well asin FIGS. 3 a and 3 b.

Finally, an activator in the processes of the present invention may alsobe a combination of at least two different activators of formula (1)and/or (2). For example two different ammonium components may be used atthe same time with the same or different NCA's. Using two differentcationic compounds in the activators according to formula (1) and/or (2)can result in broadened MWDs and a broader range of melting points inthe resulting polyolefins and can thus be used to tailor polymerproperties. For example, N-methylpyrrolidinium and trimethylammonium maybe used in combination together with the same NCA as defined below,particularly those such as tetrakis(pentafluorophenyl)borate andtetrakis(heptafluoronaphthyl)borate. Furthermore, in order to obtain thesame effect as a mixture of cationic components, an activator with onecationic component may be used, while a second Lewis base may be addedas a free base.

The Non-Coordinating Anion (NCA)

In the catalyst systems and the polymerization processes of the presentinvention [Y]⁻ in formulae (1) and (2) is a non-coordinating anion(NCA). The term “non-coordinating anion” means an anion that does notcoordinate to the metal cation of the catalyst or that does coordinateto the metal cation, but only weakly. NCA's are usually relatively large(bulky) and capable of stabilizing the active catalyst species which isformed when the compound and the activator are combined. Said anion muststill be sufficiently labile to be displaced by unsaturated monomers.Further, the anion will not transfer an anionic substituent or fragmentto the cation of the transition metal compound as to cause it to form aneutral transition metal compound and a neutral by-product from theanion. Thus, suitable NCAs are those which are not degraded toneutrality when the initially formed complex decomposes. Two classes ofcompatible NCAs useful herein have been disclosed e.g. in EP-A-0 277 003and EP-A-0277 004. They include: 1) anionic coordination complexescomprising a plurality of lipophilic radicals covalently coordinated toand shielding a central charge-bearing metal or metalloid core, and 2)anions comprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

The anion component [Y]⁻ includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2 to 6; n−k=d; M is an element selected from group 13 of thePeriodic Table of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radical, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide (but more than one q may be a halide containinggroup). Preferably, each Q is a fluorinated hydrocarbyl having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmore preferably each Q is a perfluorinated aryl group. Examples ofsuitable [Y]⁻ also include diboron compounds as those disclosed in U.S.Pat. No. 5,447,895.

[Y]⁻ is preferably [B(R⁴)₄]⁻, with R⁴ being an aryl group or asubstituted aryl group, of which the one or more substituents areidentical or different and are selected from the group consisting ofalkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups.Preferred examples of [Y]⁻ for use in the present invention are:tetraphenylborate, tetrakis(pentafluorophenyl)borate,tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tetrakis(perfluoronaphthyl)borate (also referred to astetrakis(heptafluoronaphthyl)borate), tetrakis(perfluorobiphenyl)borate,and tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Particularlypreferred [Y]⁻ are tetrakis(pentafluorophenyl)borate andtetrakis(heptafluoronaphthyl)borate.

Any of the NCA's [Y]⁻ illustrated herein can be used in combination withany cation component of the activator of formula (1) or (2) as definedhereinabove. Thus, any combination of preferred components [Y]⁻ andpreferred components [R¹R²R³AH]⁺ or [R_(n)AH]⁺ are considered to bedisclosed and suitable in the processes of the present invention.

Preferred Activators

Preferred activators of formula (1) in the catalyst systems of thepresent invention and used in the polymerization processes of thepresent invention are those wherein A is nitrogen, R¹ and R² togetherare a —(CH₂)_(a)— group with a being 3, 4, 5, or 6, and R³ is C₁, C₂,C₃, C₄ or C₅ alkyl, and [Y]⁻ is [B(R⁴)₄]⁻, with R⁴ being an aryl groupor a substituted aryl group, of which the one or more substituents areidentical or different and are selected from the group consisting ofalkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups,and preferably R⁴ is a perhalogenated aryl group, more preferably aperfluorinated aryl group, more preferably pentafluorophenyl,heptafluoronaphthyl or perfluorobiphenyl. Preferably, these activatorsare combined with transition metal compound (such as a metallocene) toform the catalyst systems of the present invention.

Preferred activators in the catalyst systems of formula (2) in thecatalyst systems used in the polymerization processes of the presentinvention are those wherein A is nitrogen, n is 3, all groups R areidentical and are methyl, ethyl or isopropyl, and [Y]⁻ is [B(R⁴)₄]⁻,with R⁴ being an aryl group or a substituted aryl group, of which theone or more substituents are identical or different and are selectedfrom the group consisting of alkyl, aryl, a halogen atom, halogenatedaryl, and haloalkylaryl groups, and preferably R⁴ is a perhalogenatedaryl group, more preferably a perfluorinated aryl group, more preferablypentafluorophenyl, heptafluoronaphthyl or perfluorobiphenyl. Preferably,these activators are combined with a transition metal compound (such asa metallocene) to form the catalyst systems of the present invention.

In the polymerization process of the present invention, in addition tothe preferred activators of formula (1) mentioned in the precedingparagraph also the activators of formula (2) wherein A is nitrogen andall groups R are identically methyl or ethyl, and wherein [Y]⁻ isdefined as in the preceding paragraph are preferably used. Again, theseactivators are preferably combined with a metallocene (e.g. as explainedherein below) to form the catalyst systems used in the polymerizationprocess of the present invention.

Transition Metal Compounds

Any transition metal compound capable of catalyzing a reaction such as apolymerization reaction, upon activation of an activator as describedabove is suitable for use in the present invention. Transition metalcompounds known as metallocenes are preferred compounds according to thepresent invention.

Metallocenes

The metallocene compounds (also referred to as metallocenes, metallocenecatalyst precursors, or catalyst precursors) useful herein are generallyknown in the art, and are preferably cyclopentadienyl derivatives oftitanium, zirconium and hafnium. Useful metallocenes (e.g. titanocenes,zirconocenes and hafnocenes) may be represented by the followingformulae:

wherein M is the metal center, and is a Group 4 metal, preferablytitanium, zirconium or hafnium, preferably zirconium or hafnium when L₁and L₂ are present and preferably titanium when Z is present; n is 0 or1;T is an optional bridging group which, if present, in preferredembodiments is selected from dialkylsilyl, diarylsilyl, dialkylmethyl,ethylenyl (—CH₂—CH₂—) or hydrocarbylethylenyl wherein one, two, three orfour of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl,where hydrocarbyl can be independently C₁ to C₁₆ alkyl or phenyl, tolyl,xylyl and the like, and when T is present, the catalyst represented canbe in a racemic or a meso form;L₁ and L₂ are the same or different cyclopentadienyl, indenyl,tetrahydroindenyl or fluorenyl rings, optionally substituted, that areeach bonded to M, or L₁ and L₂ are the same or differentcyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, which areoptionally substituted, in which any two adjacent R groups on theserings are optionally joined to form a substituted or unsubstituted,saturated, partially unsaturated, or aromatic cyclic or polycyclicsubstituent;Z is nitrogen, oxygen or phosphorus (preferably nitrogen);R′ is a cyclic linear or branched C₁ to C⁴⁰ alkyl or substituted alkylgroup (preferably Z-R′ form a cyclododecylamido group);X₁ and X₂ are, independently, hydrogen, halogen, hydride radicals,hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbylradicals, substituted halocarbyl radicals, silylcarbyl radicals,substituted silylcarbyl radicals, germylcarbyl radicals, or substitutedgermylcarbyl radicals; or both X are joined and bound to the metal atomto form a metallacycle ring containing from about 3 to about 20 carbonatoms; or both together can be an olefin, diolefin or aryne ligand.

By use of the term hafnocene is meant a bridged or unbridged, bis- ormono-cyclopentadienyl (Cp) hafnium complex having at least two leavinggroups X₁ and X₂, which are as defined immediately above and where theCp groups may be substituted or unsubstituted cyclopentadiene, indene orfluorene. By use of the term zirconocene is meant a bridged orunbridged, bis- or mono-cyclopentadienyl (Cp) zirconium complex havingat least two leaving groups X₁ and X₂, which are as defined immediatelyabove and where the Cp groups may be substituted or unsubstitutedcyclopentadiene, indene or fluorene. By use of the term titanocene ismeant a bridged or unbridged, bis- or mono-cyclopentadienyl (Cp)titanium complex having at least two leaving groups X₁ and X₂, which areas defined immediately above and where the Cp groups may be substitutedor unsubstituted cyclopentadiene, indene or fluorene.

Among the metallocene compounds which can be used in this invention arestereorigid, chiral or asymmetric, bridged or non-bridged, or so-called“constrained geometry” metallocenes. See, for example, U.S. Pat. No.4,892,851; U.S. Pat. No. 5,017,714; U.S. Pat. No. 5,132,281; U.S. Pat.No. 5,155,080; U.S. Pat. No. 5,296,434; U.S. Pat. No. 5,278,264; U.S.Pat. No. 5,318,935; U.S. Pat. No. 5,969,070; U.S. Pat. No. 6,376,409;U.S. Pat. No. 6,380,120; U.S. Pat. No. 6,376,412; WO-A-(PCT/US92/10066);WO 99/07788; WO-A-93/19103; WO 01/48034; EP-A2-0 577 581; EP-A1-0 578838; WO 99/29743 and also the academic literature, see e.g. “TheInfluence of Aromatic Substituents on the Polymerization Behavior ofBridged Zirconocene Catalysts”, Spaleck, W., et al, Organometallics1994, 13, 954-963, and “ansa-Zirconocene Polymerization Catalysts withAnnelated Ring Ligands—Effects on Catalytic Activity and Polymer ChainLengths”, Brintzinger, H., et al, Organometallics 1994, 13, 964-970, anddocuments referred to therein. The bridged metallocenes disclosed in WO99/07788 and the unbridged metallocenes disclosed in U.S. Pat. No.5,969,070 are particularly suitable for the present invention.

Preferably, the transition metal compound is a dimethylsilylbis(indenyl)metallocene, wherein the metal is a Group 4 metal, specifically,titanium, zirconium, or hafnium, and the indenyl may be substituted byone or more substituents selected from the group consisting of a halogenatom, C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅ arylalkyl, and C₆ toC₂₅ alkylaryl. More preferably, the metal is zirconium or hafnium, L₁and L₂ are unsubstituted or substituted indenyl radicals, T isdialkylsiladiyl, and X₁ and X₂ are both halogen or C₁ to C₃ alkyl.Preferably, these compounds are in the rac-form.

Illustrative, but not limiting examples of preferred stereospecificmetallocene compounds are the racemic isomers ofdimethylsilylbis(indenyl) metal dichloride, -diethyl or -dimethyl,wherein the metal is titanium, zirconium or hafnium, preferably hafniumor zirconium. It is particularly preferred that the indenyl radicals arenot substituted by any further substituents. However, in certainembodiments the two indenyl groups may also be replaced, independentlyof each other, by 2-methyl-4-phenylindenyl; 2-methyl indenyl;2-methyl,4-[3′,5′-di-t-butylphenyl]indenyl;2-ethyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-n-propyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-iso-propyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-iso-butyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-n-butyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-sec-butyl-4-[3′,5′-di-t-butylphenyl]indenyl;2-methyl-4-[3′,5′-di-phenylphenyl]indenyl;2-ethyl-4-[3′,5′-di-phenylphenyl]indenyl;2-n-propyl-4-[3′,5′-di-phenylphenyl]indenyl;2-iso-propyl-4-[3′,5′-di-phenylphenyl]indenyl;2-n-butyl-4-[3′,5′-di-phenylphenyl]indenyl;2-sec-butyl-4-[3′,5′-di-phenylphenyl]indenyl;2-tert-butyl-4-[3′,5′-di-phenylphenyl]indenyl; and the like. Furtherillustrative, but not limiting examples of preferred stereospecificmetallocene compounds are the racemic isomers of9-silafluorenylbis(indenyl) metal dichloride, -diethyl or -dimethyl,wherein the metal is titanium, zirconium or hafnium. Again,unsubstituted indenyl radicals are particularly preferred. In someembodiments, however the two indenyl groups may be replaced,independently of each other, by any of the substituted indenyl radicalslisted above.

Particularly preferred metallocenes as transition metal compounds foruse in the catalyst systems of the present invention together with theactivators of formula (1) or (2) defined above for use in polymerizingolefins are rac-dimethylsilylbis(indenyl) hafnocenes or -zirconocenes,rac-dimethylsilylbis(2-methyl-4-phenylindenyl) hafnocenes or-zirconocenes, rac-dimethylsilylbis(2-methyl-indenyl) hafnocenes or-zirconocenes, and rac-dimethylsilylbis(2-methyl-4-naphthylindenyl)hafnocenes or -zirconocenes, wherein the hafnium and zirconium metal issubstituted, in addition to the bridged bis(indenyl) substituent, by twofurther substituents, which are halogen, preferably chlorine or bromineatoms, or alkyl groups, preferably methyl and/or ethyl groups.Preferably, these additional substituents are both chlorine atoms orboth methyl groups. Particularly preferred transition metal compoundsare dimethylsilylbis(indenyl)hafnium dimethyl,rac-dimethylsilylbis(indenyl)zirconium dimethyl,rac-ethylenylbis(indenyl)zirconium dimethyl, andrac-ethylenylbis(indenyl)hafnium dimethyl.

Illustrative, but not limiting examples of preferred non-stereospecificmetallocene catalysts are:[dimethylsilanediyl(tetramethylcyclopentadienyl)-(cyclododecylamido)]metaldihalide,[dimethylsilanediyl(tetramethylcyclopentadienyl)(t-butylamido)]metaldihalide,[dimethylsilanediyl(tetramethylcyclopentadienyl)(exo-2-norbornyl)]metaldihalide, wherein the metal is Zr, Hf, or Ti, preferably Ti, and thehalide is preferably chlorine or bromine.

In a preferred embodiment, the transition metal compound is a bridged orunbridged bis(substituted or unsubstituted indenyl) hafnium dialkyl ordihalide.

Finally, also non-metallocene compounds that are active in catalyzingolefin polymerization reactions are suitable as the transition metalcompound in the catalyst systems and the processes of the presentinvention. A particularly preferred species of non-metallocene catalystsare the pyridyl amines disclosed e.g. in WO 03/040201.

Preferred Catalyst Systems

Preferred combinations of transition metal compound and activator in thecatalyst systems for olefin polymerization according to the presentinvention comprise the following components:

-   a metallocene compound, preferably a dialkylsilyl-bridged    bis(indenyl) metallocene, wherein the metal is a group 4 metal and    the indenyl is unsubstituted, or if substituted, is substituted by    one or more substituents selected from the group consisting of a C₁    to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅ arylalkyl, and C₆ to C₂₅    alkylaryl; more preferably dimethylsilylbis(indenyl) metal    dichloride or -dimethyl, ethylenylbis(indenyl) metal dichloride or    -dimethyl, dimethylsilylbis(2-methyl-4-phenylindenyl) metal    dichloride or -dimethyl, dimethylsilylbis(2-methyl-indenyl) metal    dichloride or -dimethyl, and    dimethylsilylbis(2-methyl-4-naphthylindenyl) metal dichloride or    -dimethyl, wherein in all cases the metal may be zirconium or    hafnium,-   a cationic component [R¹R²R³AH]⁺ wherein preferably A is nitrogen,    R¹ and R² are together an —(CH₂)_(a)— group, wherein a is 3, 4, 5 or    6 and form, together with the nitrogen atom, a 4-, 5-, 6- or    7-membered non-aromatic ring to which, via adjacent ring carbon    atoms, optionally one or more aromatic or heteroaromatic rings may    be fused, and R³ is C₁, C₂, C₃, C₄ or C₅ alkyl, more preferably    N-methylpyrrolidinium or N-methylpiperidinium; or a cationic    component [R_(n)AH]⁺ wherein preferably A is nitrogen, n is 3 and    all R are identical and are C₁ to C₃ alkyl groups, more preferably    trimethylammonium or triethylammonium; and-   an anionic component [Y]⁻ which is an NCA, preferably of the formula    [B(R⁴)₄]⁻, with R⁴ being an aryl group or a substituted aryl group,    of which the one or more substituents are identical or different and    are selected from the group consisting of alkyl, aryl, a halogen    atom, halogenated aryl, and haloalkylaryl groups, preferably    perhalogenated aryl groups, more preferably perfluorinated aryl    groups, and more preferably pentafluorophenyl, heptafluoronaphthyl    or perfluorobiphenyl.

More preferably, the activator for use in any of the polymerizationprocesses according to the present invention is trimethylammoniumtetrakis(pentafluorophenyl)borate, N-methylpyrrolidiniumtetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(heptafluoronaphthyl)borate, or N-methylpyrrolidiniumtetrakis(heptafluoronaphthyl) borate. The metallocene is preferablyrac-dimethylsilyl bis(indenyl)zirconium dichloride or -dimethyl,rac-dimethylsilyl bis(indenyl)hafnium dichloride or -dimethyl,rac-ethylenyl bis(indenyl)zirconium dichloride or -dimethyl orrac-ethylenyl bis(indenyl)hafnium dichloride or -dimethyl.

In another embodiment, a preferred transition metal compound comprises abis indenyl compound represented by the formula:

wherein M is a group 4 metal, preferably hafnium, T is a bridging group(such as an alkylene (methylene, ethylene) or a di substituted silyl orgermyl group, (such as dimethyl silyl)), n is 0 or 1, R₂, R₃, R₄, R₅,R₆, and R₇ are hydrogen, a heteroatom, a substituted heteroatom group, asubstituted or unsubstituted alkyl group, and a substituted orunsubstituted aryl group (preferably a substituted or unsubstitutedalkyl or a substituted or unsubstituted aryl group). In a preferredembodiment R₂ is hydrogen. In another preferred embodiment R₂ and R₄ arehydrogen. In another preferred embodiment R₂ is hydrogen and R₄ is C₁ toC₂₀ alkyl (preferably methyl) or an aryl group (such as substituted orunsubstituted phenyl). In another preferred embodiment R₂ and R₄ aremethyl. In another embodiment R₂ and R₄ are not methyl. In anotherembodiment R₂ is not methyl. In another preferred embodiment, R₃, R₄,R₅, R₆, and R₇ are hydrogen and R₂ is substituted or unsubstituted alkylor substituted or unsubstituted aryl (preferably methyl). In anotherpreferred embodiment, R₂, R₃, R₅, R₆, and R₇ are hydrogen and R₄ issubstituted or unsubstituted alkyl or substituted or unsubstituted aryl(preferably methyl or phenyl).

Any catalyst system resulting from any combination of the preferredmetallocene compound, preferred cationic component of the activator andpreferred anionic component of the activator mentioned in the precedingparagraph shall be explicitly disclosed and may be used in accordancewith the present invention in the polymerization of one or more olefinmonomerse. Also, combinations of two different activators can be usedwith the same or different metallocene(s).

Scavengers or Additional Activators

The catalyst systems suitable for all aspects of the present inventionmay contain, in addition to the transition metal compound and theactivator described above, also additional (additional activators orscavengers) as explained in the following.

A co-activator is a compound capable of alkylating the transition metalcomplex, such that when used in combination with an activator, an activecatalyst is formed. Co-activators include alumoxanes as mentioned in thefollowing, and aluminum alkyls as further listed below. An alumoxane ispreferably an oligomeric aluminum compound represented by the generalformula (R^(x)—Al—O)_(n), which is a cyclic compound, or R^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. Most commonalumoxane is a mixture of the cyclic and linear compounds. In thegeneral alumoxane formula, R^(x) is independently a C₁-C₂₀ alkylradical, for example, methyl, ethyl, propyl, butyl, pentyl, isomersthereof, and the like, and “n” is an integer from 1-50. More preferably,R^(x) is methyl and “n” is at least 4. Methyl alumoxane (MAO) as well asmodified MAO, referred to herein as MMAO, containing some higher alkylgroups to improve the solubility, ethyl alumoxane, iso-butyl alumoxaneand the like are useful herein. Particularly useful MAO can be purchasedfrom Albemarle in a 10 wt % solution in toluene. Co-activators aretypically only used in combination with Lewis acid activators and ionicactivators when the pre-catalyst is not a dihydrocarbyl or dihydridecomplex.

In some embodiments of the invention, scavengers may be used to “clean”the reaction of any poisons that would otherwise react with the catalystand deactivate it. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is a C₁-C₂₀ alkyl radical, for example, methyl,ethyl, propyl, butyl, pentyl, and isomers thereof, and each Z isindependently R^(x) or a different univalent anionic ligand such ashalogen (Cl, Br, I), alkoxide (OR^(x)) and the like. More preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,ethylaluminium dichloride, tri-iso-butylaluminum, tri-n-octylaluminum,tri-n-hexylaluminum, trimethylaluminum and combinations thereof.Preferred boron alkyls include triethylboron. Scavenging compounds mayalso be alumoxanes and modified alumoxanes including methylalumoxane andmodified methylalumoxane.

Method of Preparing Catalyst System

The catalyst systems of the present invention can be prepared accordingto methods known in the art. For obtaining the cations of the activatorsof formula (1) or (2) as defined hereinabove, for example ammoniumcations can be provided as salts that can be synthesized by the reactionof an amine with an acid in which the conjugate base of the acid remainsas the counteranion or is exchanged with other anions. See “OrganicChemistry”, Pine et al. 4^(th) edition, McGraw-Hill, 1980. A usefulsynthesis for example is the reaction of a slight excess of HCl (as anEt₂O solution) with the amine in hexanes resulting in the immediateprecipitation of the amine hydrochloride. The chloride can be replacedby anion exchange with a suitable NCA according to the presentinvention. See references Chemische Berichte, 1955, 88, p. 962, or U.S.Pat. No. 5,153,157 and references therein. Phosphines and ethers aresimilarly protonated with acids and can undergo anion exchange reactionsto the desired phosphonium salts, see for example DE 2116439.

Supports

Preferably the catalyst systems of this invention include a supportmaterial or carrier. The support material is any of the conventionalsupport materials. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferred support materials are inorganic oxides that include Group 2,3, 4, 5, 13 or 14 metal oxides. Preferred supports include silica, whichmay or may not be dehydrated, fumed silica, alumina (WO 99/60033),silica-alumina and mixtures thereof. Particularly useful supportsinclude magnesia, titania, zirconia, montmorillonite (European PatentEP-B1 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No.6,034,187) and the like. Also, combinations of these support materialsmay be used, for example, silica-chromium, silica-alumina,silica-titania and the like.

It is preferred that the support material, more preferably an inorganicoxide, have a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.More preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the carrier useful in the invention typically haspore size in the range of from 10 to 1000 Å, preferably 50 to about 500Å, and more preferably 75 to about 350 Å.

In another embodiment the support may comprise one or more types ofsupport material, which may be treated differently. For example onecould use two different silicas that had different pore volumes or hadbeen calcined at different temperatures. Likewise one could use silicathat had been treated with a scavenger or other additive and silica thathad not.

Preferably the supports have been calcined at temperatures above 500°C., preferably above 550° C., preferably at 600° C. or above, preferablyabove 650° C., preferably at 700° C. or above, preferably above 750° C.,preferably at 800° C. or above.

In an alternate embodiment, the supports have been calcined attemperatures above 200° C., preferably above 300° C., preferably at 400°C. or above.

In another embodiment, the supports have not been calcined.

Method of Supporting Catalyst System

The catalyst systems of the invention are supported on a suitablesupport as explained hereinabove according to the methods known in theart. Typically a support is first modified with reagents that react withhydroxy groups to render these less reactive with the cationictransition metal complex. Such reagents would include aluminum alkylssuch as AlEt₃, Al^(i)Bu₃, etc. Other reagents would include MMAO, MAO,silanes containing Si—H, chloro-silanes of the general formulaR_(x)SiCl_(y), Si—OEt compounds, etc. The activator of formula (1) or(2) can then be reacted with the transition metal compound, preferablythe metallocene, in a separate step and then supported on the modifiedsupport. Also, the transition metal compound, preferably themetallocene, can be supported first on the modified support followed bythe activator. Alternatively, the activator is supported first on themodified supported, followed by the transition metal compound (themetallocene).

Monomers

The catalyst systems described herein can be used for the polymerizationof one or more olefin monomers. Typical monomers include unsaturatedmonomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbonatoms, and more preferably 2 to 8 carbon atoms. Useful monomers includelinear, branched or cyclic olefins; linear branched or cyclic alphaolefins; linear, branched or cyclic diolefins; linear branched or cyclicalpha-omega diolefins; and linear, branched or cyclic polyenes.Preferred monomers include one or more of ethylene, propylene, butene-1,pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-pentene-1, norbornene, norbornadiene, vinyl norbornene, andethylidene norbornene monomers.

In one embodiment the process of this invention relates to thehomopolymerization of ethylene or the copolymerization of ethylene withat least one comonomer having from 3 to 8 carbon atoms, preferably 4 to7 carbon atoms. Particularly, the comonomers are propylene, butene-1,4-methyl-pentene-1, 3-methyl-pentene-1, hexene-1 and octene-1, the morepreferred being hexene-1, butene-1 and octene-1. Preferably thecomonomer(s) are present in the ethylene copolymer at from 0.1 to 50 mol%, preferably 1 to 30 mol %, preferably 1 to 20 mol %.

In another, preferred embodiment the process of this invention relatesto the homopolymerization of propylene or the copolymerization ofpropylene. In the case of copolymerization, the comonomer of thecopolymer is preferably ethylene and/or a C₄ to C₂₀ linear, branched orcyclic monomer, and in one embodiment is a C₄ to C₁₂ linear or branchedalpha-olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, dodecene, 4-methyl-pentene-1, 3-methyl pentene-1,3,5,5-trimethyl-hexene-1, and the like. The comonomer, preferablyethylene, is present in from 0.5 to 99 mol %, preferably from 1 to 60mol %, more preferably from 1 to 50 mol %, more preferably from 1 to 35mol %, more preferably from 2 to 30 mol %, more preferably from 2 to 25mol %, and more preferably from 2 to 15 mol %, based on the entirepolymer.

In another embodiment the polymer produced herein is a homopolymer orcopolymer of one or more linear or branched C₃ to C₃₀ prochiralalpha-olefins or C₅ to C₃₀ ring containing olefins or combinationsthereof capable of being polymerized by either stereospecific andnon-stereospecific catalysts. Prochiral, as used herein, refers tomonomers that favor the formation of isotactic or syndiotactic polymerwhen polymerized using stereospecific catalyst(s).

In another embodiment, the monomer to be polymerized comprisesaromatic-group-containing monomers containing up to 30 carbon atoms.Suitable aromatic-group-containing monomers comprise at least onearomatic structure, preferably from one to three, more preferably aphenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C₁ to C₁₀ alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also useful monomersherein. These monomers can contain up to 30 carbon atoms. Suitablenon-aromatic cyclic group containing monomers preferably have at leastone polymerizable olefinic group that is either pendant on the cyclicstructure or is part of the cyclic structure. The cyclic structure mayalso be further substituted by one or more hydrocarbyl groups such as,but not limited to, C₁ to C₁₀ alkyl groups. Preferred non-aromaticcyclic group containing monomers include vinylcyclohexane,vinylcyclohexene, vinylnorbornene, ethylidene norbornene,cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantaneand the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, more preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In a preferred embodiment one or more dienes are present in the ethyleneand/or propylene-based polymer produced herein at up to 10 weight %,preferably at 0.00001 to 1.0 weight %, preferably 0.002 to 0.5 weight %,even more preferably 0.003 to 0.2 weight %, based upon the total weightof the polymer. In some embodiments 500 ppm or less of diene is added tothe polymerization, preferably 400 ppm or less, preferably or 300 ppm orless, based upon the total weight of the polymer. In other embodimentsat least 50 ppm of diene is added to the polymerization, or 100 ppm ormore, or 150 ppm or more, based upon the total weight of the polymer.

In another embodiment ethylene and/or propylene is/are polymerized withat least two different comonomers to form a terpolymer. Preferredcomonomers include a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. Preferred terpolymers includeethylene/butene-1/hexene-1, ethylene/propylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/octene-1,ethylene/propylene/norbornene and the like.

More preferably, the process of the present invention is for thepolymerization of propylene to form homopolypropylene or together withanother monomer, preferably ethylene, to form propylene copolymers.

Polymerization Processes

The present invention also relates to a process for polymerizing one ormore olefins, preferably propylene, either alone or in the presence ofanother comonomer, such as ethylene, the process comprising contactingunder polymerization conditions one or more olefin monomers with acatalyst system comprising an activator of formula (1) as defined above.Thus, analogously, the present invention also relates to the use of acompound of formula (1) as defined above as an activator in a catalystsystem for the polymerization of one or more olefins, preferablypropylene, either alone or in the presence of another comonomer, such asethylene.

Additionally, the present invention relates to a process forpolymerizing one or more olefins, preferably propylene, either alone orin the presence of another comonomer, such as ethylene, the processcomprising contacting under polymerization conditions one or more olefinmonomers with a catalyst system comprising an activator of formula (2)as defined above. One characteristic of this process is that the Mw ofthe polymer formed increases or at least does not substantially decreasewith increasing monomer conversion at one given reaction temperature.For the purposes of this invention, by stating that at a given reactiontemperature the weight average molecular weight (Mw) of the polymerformed increases or at least does not substantially decrease withincreasing monomer conversion it is meant that the slope of the Mwversus the monomer conversion is positive or essentially zero over theentire range of monomer conversion. To quantify, with the processes andthe catalyst systems of the present invention the Mw does not decreasemore than 20%, preferably the Mw does not decrease more than 15%, morepreferably the Mw does not decrease more than 9%, and more preferablythe Mw does not decrease more than 5% for each further 5% of monomerconversion. Increased conversion can be achieved by means of a lowmonomer concentration in the feed, a higher catalyst concentration orsimply by longer reaction times.

In the processes of the present invention, using a catalyst systemcomprising an activator of formula (1) or (2) in combination with atransition metal compound propylene homo- or copolymers can be obtainedthat have high melting points and/or high Mw.

The catalyst systems described above are suitable for use in a solution,bulk, gas or slurry polymerization process or a combination thereof,preferably solution phase or bulk phase polymerization process.Preferably the process is a continuous process. By continuous is meant asystem that operates without interruption or cessation. For example acontinuous process to produce a polymer would be one where the reactantsare continually introduced into one or more reactors and polymer productis continually withdrawn.

In one embodiment, this invention is directed toward the solution, bulk,slurry or gas phase polymerization reactions involving thepolymerization of one or more of monomers as defined above. Preferably ahomopolypropylene or a copolymer of propylene and ethylene and/or moreother alpha-olefins or diolefins as listed above is produced.

One or more reactors in series or in parallel may be used in the presentinvention. Catalyst precursor and activator may be delivered as asolution or slurry, either separately to the reactor, activated in-linejust prior to the reactor, or preactivated and pumped as an activatedsolution or slurry to the reactor. A preferred operation is twosolutions activated in-line. For more information on methods tointroduce multiple catalysts into reactors, please see U.S. Pat. No.6,399,722, and WO 01/30862A1. While these references may emphasize gasphase reactors, the techniques described are equally applicable to othertypes of reactors, including continuous stirred tank reactors, slurryloop reactors and the like. Polymerizations are carried out in eithersingle reactor operation, in which monomer, comonomers,catalyst/activator, scavenger, and optional modifiers are addedcontinuously to a single reactor or in series reactor operation, inwhich the above components are added to each of two or more reactorsconnected in series. The catalyst compounds can be added to the firstreactor in the series. The catalyst component may also be added to bothreactors, with one component being added to first reaction and anothercomponent to other reactors.

In one embodiment 500 ppm or less (wt basis) of hydrogen is added to thepolymerization reactor, or 400 ppm or less, or 300 ppm or less. In otherembodiments at least 50 ppm of hydrogen is added to the polymerizationmixture, or 100 ppm or more, or 150 ppm or more.

One characteristic feature of the olefin polymerization processaccording to the present invention comprising the use of the catalystsystems having activators of formula (1) or (2) according to the presentinvention is that, at one given reaction temperature the Mw of thepolymer formed increases (or at least does not substantially decrease,as explained above) with increasing monomer conversion. This isillustrated in FIG. 1. This behavior is quite different from knownpolymerization processes using conventional catalyst systems, where—incontrast to the present invention—the slope of the Mw versus the monomerconversion is usually negative. Again, without wishing to be bound bythis theory, it is believed that the balanced coordination strength (orbasicity) of the Lewis base originating from the proton-depletedcationic component of the activator is the reason for this unusualcharacteristic.

The fact that higher Mw polymers can be produced at higher monomerconversion rates means that the conversion can be increased incommercial reactors, e.g. by using low monomer concentration in the feedor long run times, by using a higher catalyst concentration, or byraising the reaction temperature, which makes them more efficient byreducing the monomer concentration in the effluent and reducingoperation cost associated with monomer separation and recirculation. Inmany processes to date, conversion rate is controlled in order to keepthe Mw (and the melting point) of the resulting polymer sufficientlyhigh, which had a limiting effect on the quantity of the productionoutput. This limitation is overcome or at least alleviated by thepresent invention.

This effect is particularly shown by the less substituted metallocenesused together with the more coordinating amines, such as byrac-dimethylsilylbisindenylhafnium dimethyl,rac-dimethylsilylbisindenylzirconium dimethyl,rac-dimethylgermylbisindenylhafnium dimethyl,rac-ethylenebisindenylhafnium dimethyl, rac-ethylenebisindenylzirconiumdimethyl. More substituted metallocenes may show this effect with highlycoordinating amines.

Depending on which monomer(s) is/are to be polymerized, variouspolymerization processes (gas phase, slurry phase, solutionpolymerization) may be used in connection with the present invention.

Gas Phase Polymerization

Generally, in a fluidized gas bed process useful herein for producingpolymers, a gaseous stream containing one or more monomers iscontinuously cycled through a fluidized bed in the presence of acatalyst under reactive conditions. The gaseous stream is withdrawn fromthe fluidized bed and recycled back into the reactor. Simultaneously,polymer product is withdrawn from the reactor and fresh monomer is addedto replace the polymerized monomer. See for example U.S. Pat. Nos.4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922;5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst system are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. Preferably, a hexane or an isobutane medium isemployed.

In one embodiment, a preferred polymerization technique useful in theinvention is referred to as a particle form polymerization or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is described in U.S. Pat. No.3,248,179, which is fully incorporated herein by reference. A preferredtemperature in the particle form process is within the range of about85° C. to about 110° C. Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

In the slurry process useful in the invention the total reactor pressureis in the range of from 400 psig (2758 kPa) to 800 psig (5516 kPa),preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), morepreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa). Theconcentration of predominant monomer in the reactor liquid medium may bein the range of from about 1 to 10 weight percent, preferably from about2 to about 7 weight percent, more preferably from about 2.5 to about 6weight percent, more preferably from about 3 to about 6 weight percent.

Homogeneous, Bulk, or Solution Phase Polymerization

The catalyst systems described herein can be used advantageously inhomogeneous solution processes. Generally this involves polymerizationin a continuous reactor in which the polymer formed and the startingmonomer and catalyst materials supplied are agitated to reduce or avoidconcentration gradients. Some useful processes operate above the cloudpoint of the polymers at high pressures. Reaction environments includethe case where the monomer(s) acts as diluent or solvent as well as thecase where a liquid hydrocarbon is used as diluent or solvent. Preferredhydrocarbon liquids include both aliphatic and aromatic fluids such asdesulphurized light virgin naphtha and alkanes, such as propane,isobutene, mixed butanes, hexane, pentane, isopentane, isohexane,cyclohexane, isooctane, and octane.

Temperature control in the reactor is typically obtained by balancingthe heat of polymerization with reactor cooling by reactor jackets orcooling coils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature also dependson the catalyst used. In general, the reactor temperature is in therange from about 30° C. to about 250° C., preferably from about 60° C.to about 200° C., more preferably from about 70° C. to about 180° C.,more preferably from about 80° C. to about 160° C., and more preferablyfrom about 100° C. to about 140° C. Polymerization temperature may varydepending on catalyst choice. In series operation, the second reactortemperature is preferably higher than the first reactor temperature. Inparallel reactor operation, the temperatures of the two reactors areindependent. The pressure is generally in the range from atmosphericpressure up to high pressures such as about 300 MPa, about 200 MPa orabout 100 MPa. Also lower pressures up to about 50, about 40, about 30,about 20 or about 15 MPa are suitable. The lower end of the possiblepressure range may be anything from about 0.1 MPa, such as 0.5 MPa,about 1 MPa or about 2.0 MPa. The monomer concentration in the reactor(based on the entire reaction mixture) may be anywhere from very diluteup to using the monomer as the solvent (e.g. polymerizing propylene inbulk propylene). Suitable monomer concentrations may be, for example upto about 2 mol/L, up to about 5 mol/L, up to about 10 mol/L, or evenhigher, such as up to about 15 mol/L.

In one embodiment 500 ppm or less of hydrogen is added to thepolymerization mixture, or 400 ppm or less or 300 ppm or less. In otherembodiments at least 50 ppm of hydrogen is added to the polymerizationmixture, or 100 ppm or more, or 150 ppm or more.

Each of these processes may also be employed in single reactor, parallelor series reactor configurations in a suitable diluent or solvent.Hydrocarbon solvents are suitable, both aliphatic and aromatic. Alkanes,such as n- or isohexane, pentane, isopentane, and octane, are preferred.Also, chlorinated or fluorinated hydrocarbons may be used as solvents.Suitable fluorinated hydrocarbons listed in WO 2004/058828.

Finally, all polymerization conditions specifically disclosed in WO2004/026921, WO 2004/056953 and U.S. Provisional Application No.60/933,007, which are incorporated herein by reference, may be used inthe processes of the present invention.

Preferred Polymerization Process

Preferably, the polymerization processes according to the presentinvention using activators of formula (1) or (2) in combination with atransition metal compound, preferably a metallocene, are solutionprocesses, wherein polymerization is conducted at a temperature of atleast about 60° C., preferably at least about 80° C., more preferably ofat least about 100° C., more preferably of at least about 120° C., morepreferably at least about 140° C. Preferably, the polymerizationprocesses according to the present invention using activators of formula(1) and/or (2) in combination with a metallocene as described above arerun with a monomer conversion of from 5 to 95%, alternately 5 to 95%,alternately from 5 to 90%, alternately from 5 to 85%, alternately from 5to 80%, alternately from 5 to 75%, alternately from 5 to 70%,alternately from 5 to 65%, alternately from 5 to 60%, alternately from7.5 to 60%, alternately from 7.5 to 55%, alternately from 7.5 to 50%,and alternately from 10 to 50%, all percentage being based on thetheoretically possible 100% conversion. For the purposes of the presentinvention the conversion is calculated on a weight basis (the actualamount (weight in gram) polymer obtained, divided through thetheoretically possible amount (again weight in gram) of polymer if allmonomer was converted into polymer). As an example, as propylene has adensity of 0.52 g/mL, if 100 mL propylene monomer is fed into thereactor, theoretically 52 g polypropylene could be obtained (assuming atheoretical 100% conversion). The % conversion achieved in a particularpolypropylene reaction run with 100 mL of propylene feed is thereforecalculated as follows: conversion [%]=(actual weight (g) polypropylenerecovered/52 g)×100%. So, for example, if 5.2 g of polymer arerecovered, the conversion would be 10%.

Particularly preferred polymerization processes according to the presentinvention include the following:

-   A process for polymerizing one or more olefins, preferably    propylene, optionally in combination with another olefin comonomer,    the process comprising contacting under polymerization conditions    one or more olefin monomers with a catalyst system comprising an    activator of formula (1) are defined above and are a separate aspect    of the present invention. Preferred metallocenes for use in    combination with the preferred activators of formula (1) are also    disclosed above. Preferred activators of formula (1) and preferred    metallocenes for use in this process are disclosed hereinabove.    Preferably, in this process the polymerization is conducted in    (homogeneous) solution and at a temperature of at least about 80°    C., preferably of at least about 100° C., more preferably of at    least about 120° C. The solvent may either be an alkane, or it may    be the olefin (propylene) itself.-   A process for polymerizing one or more olefins, preferably    propylene, optionally in combination with one or more other olefin    comonomer(s), the process comprising contacting under polymerization    conditions one or more olefin monomers with a catalyst system    comprising a metallocene and an activator of formula (2) as defined    above, wherein the Mw of the polymer formed increases with    increasing monomer conversion at a given reaction temperature.    Preferred activators of formula (2) and preferred metallocenes are    disclosed hereinabove. A particularly preferred activator of    formula (2) in this process is trimethylammonium tetrakis    (pentafluorophenyl) borate or trimethylammonium tetrakis    (heptafluoronaphthyl) borate. Particularly preferred metallocenes in    combination with this preferred activator of formula (2) are    rac-dimethylsilyl bis(indenyl) zirconium dimethyl and -dichloride,    rac-dimethylsilyl bis(indenyl) hafnium dimethyl, rac-ethylenyl    bis(indenyl)zirconiumdimethyl and -dichloride, and rac-ethylenyl    bis(indenyl)hafniumdimethyl and -dichloride. Also in this process    using an activator of formula (2) preferably the polymerization is    conducted in solution (typically homogeneous) and at a temperature    of at least about 80° C. to about 200° C., preferably of at least    about 100° C. to about 180° C., more preferably of at least about    120° C. The solvent may either be an n- or iso-alkane, or it may be    the olefin (such as propylene) itself. Preferably, the monomer    (preferably propylene) conversion is from 5 to 95%, more preferably    from 5 to 85%, and more preferably from 5 to 50%, the conversion    being calculated based on the amount of monomer in the feed and the    amount of monomer converted in the reactor. The monomer    concentration is generally 5 weight % or more, such as 10 weight %    or more, 20 weight % or more, or 30 weight % or more, based on the    total weight of the polymerization medium including solvent,    monomers and polymers produced.

Polymer Products

The polymers produced herein include homopolymer and copolymers ofethylene and/or propylene with optional other monomers. The polymers areobtainable by the processes as described above. Preferably, the polymersare propylene-based polymers, optionally with ethylene and/or otheralpha-olefin comonomers being present.

The polymers, especially the propylene-based polymers, produced with thepolymerization processes according to the present invention (and usingthe catalyst systems according to the present invention comprisingactivators of formula (1) and/or (2)) may have higher melting points anda higher Mw than polymers prepared by comparative processes usingconventional catalyst systems at the same reaction temperature. See inthis regard FIGS. 2 a and 2 b, and 3 a and 3 b. For example, withreference to FIGS. 2 a and 2 b, it is illustrated that the choice of thecatalyst system, and in particular the cationic component of theactivator in said catalyst system, influences the Mw and the meltingpoint of the resulting polymer achieved at a certain reactiontemperature. It is evident that with the catalyst system according tothe invention, wherein the activator is of formula (1) or formula (2) asdefined above, the resulting polymer has higher Mw and a higher meltingpoint than with a comparable conventional activator in combination withthe same metallocene compound. The same is also evident from FIGS. 3 aand 3 b. As explained above, without wishing to be bound by this theory,it is believed that the coordination strength of the Lewis baseresulting from the proton-depleted cationic component of the activatoris of importance and is balanced in order to achieve an optimal effect.

The polymers of the invention generally have an Mw (weight averagemolecular weight in g/mol) of at least about 10,000 preferably of atleast 20,000, more preferably of at least 30,000, but may also have ahigher Mw of at least 50,000, preferably at least 70,000, morepreferably at least 100,000, more preferably at least 120,000, morepreferably at least 130,000, more preferably at least 140,000, and morepreferably at least 150,000.

The polymers described herein generally have an Mw/Mn (polydispersity,PDI, MWD) of between 1 and 20, preferably from 1.5 to 15, morepreferably from 1.6 to 10, more preferably from 1.7 to 6, morepreferably from 1.9 to 4.5 and more preferably from 2 to 3.

The polymers described herein preferably have a melting point of least75° C., preferably at least 85° C., more preferably at least 90° C.,more preferably at least 100° C., more preferably at least 110° C., morepreferably at least 120° C., more preferably at least 130° C., morepreferably at least 135° C., and more preferably at least 140° C.

The polymers, preferably the propylene-based polymers, of the presentinvention preferably have a melting point of at least 70° C. and aweight average molecular weight (Mw) of at least 10,000, preferably amelting point of at least 90° C. and a Mw of at least 35,000, morepreferably a melting point of at least 100° C. and a Mw of at least50,000.

The polymers of the present invention, generally have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and more preferably greater than 0.915 g/cc.

In a preferred embodiment the polymer produced comprises at least 50weight % propylene, preferably at least 60% propylene, alternatively atleast 70% propylene, alternatively at least 80% propylene.

In another preferred embodiment the polymer produced, comprisescomonomer in from 0.1 to 99 mol %, preferably from 0.1 to 50 mol %, morepreferably from 1 to 35 mol %, more preferably from 0.2 to 30 mol %,more preferably from 0.2 to 15 mol %, and more preferably from 0.2 to 10mol %, based on the entire polymer.

Applications and End-Uses

The polymers produced by the processes of the invention are useful inmaking a wide variety of products and useful in many end-useapplications. The polymers produced by the processes of the inventioninclude linear low density polyethylenes, elastomers, plastomers, highdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers, such as impact and random copolymers.

Polymers produced by the process of the invention are useful in suchforming operations as film, sheet, and fiber extrusion and co-extrusionas well as blow molding, injection molding and rotary molding. Filmsinclude blown or cast films formed by coextrusion or by lamination,shrink film, cling film, stretch film, sealing films, oriented films.The films are useful in snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, geomembranes, and pond liners.Molded articles include single and multi-layered constructions in theform of bottles, tanks, large hollow articles, rigid food containers andtoys, etc. Polymers with low molecular weight can also be used foradhesive applications, particularly for hot melt adhesives.

In another embodiment, this invention relates to:

1. A catalyst system comprising a transition metal compound and anactivator, the activator having the formula (1):

[R¹R²R³AH]⁺ [Y]⁻,   (1)

wherein [Y]⁻ is a non-coordinating anion (NCA),A is nitrogen or phosphorus,R¹ and R² are hydrocarbyl groups or heteroatom-containing hydrocarbylgroups and together form a first, 3- to 10-membered non-aromatic ringwith A, wherein any number of adjacent ring members may optionallymembers of at least one second, aromatic or aliphatic ring or aliphaticand/or aromatic ring system of two or more rings, wherein said at leastone second ring or ring system is fused to said first ring, and whereinany atom of the first and/or at least one second ring or ring system isa carbon atom or a heteroatom and may be substituted independently byone or more substituents selected from the group consisting of ahydrogen atom, halogen atom, C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅arylalkyl, and C₆ to C₂₅ alkylaryl, andR³ is a hydrogen atom or C₁ to C₁₀ alkyl, or R³ is a C₁ to C₁₀ alkylenegroup that connects to said first ring and/or to said at least onesecond ring or ring system.2. The catalyst system of paragraph 1, wherein A is nitrogen, R¹ and R²together are a —(CH₂)_(a)— group with a being 3, 4, 5 or 6, and R³ is C₁to C₅ alkyl.3. The catalyst system of paragraph 1 or 2, wherein [Y]⁻ is [B(R⁴)₄]⁻,with R⁴ being an unsubstituted aryl group or a substituted aryl group,of which the one or more substituents are identical or different and areselected from the group consisting of C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, ahalogen atom, preferably fluorine, halogenated C₁ to C₁₀ alkyl,halogenated C₅ to C₁₅ aryl, halogenated C₆ to C₂₅ alkylaryl, andhalogenated C₆ to C₂₅ arylalkyl groups, and wherein R⁴ is preferablyperfluorinated aryl, more preferably pentafluorophenyl,heptafluoronaphthyl or perfluorobiphenyl.4. The catalyst system of any paragraphs 1 to 3, wherein the transitionmetal compound is a metallocene, preferably adialkylsiladiylbis(indenyl) metallocene, wherein the metal is a group 4metal and the indenyl is unsubstituted or substituted by one or moresubstituents selected from the group consisting of a halogen atom, C₁ toC₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅ arylalkyl, and C₆ to C₂₅ alkylaryl,and the metallocene is more preferably selected from the groupconsisting of a rac-dimethylgermylbis(indenyl)hafnocene or -zirconocene,a rac-dimethylsilyl bis(indenyl) hafnocene or -zirconocene, arac-dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-indenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-4-naphthylindenyl)hafnocene or -zirconocene, or a rac-ethylenyl bis(indenyl) hafnocene or-zirconocene, wherein the hafnocene and zirconocene has at least twoleaving groups X₁ and X₂ which are, independently, hydrogen, halogen,hydride radicals, hydrocarbyl radicals, substituted hydrocarbylradicals, halocarbyl radicals, substituted halocarbyl radicals,silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbylradicals, or substituted germylcarbyl radicals; or both X are joined andbound to the metal atom to form a metallacycle ring containing fromabout 3 to about 20 carbon atoms; or both together can be an olefin,diolefin or aryne ligand.5. The catalyst system of any of paragraphs 1 to 4, wherein thetransition metal compound and/or the activator are supported on a solidsupport, wherein the support comprises silica or alumina.6. A process for polymerizing one or more olefins, comprising contactingunder polymerization conditions one or more olefin monomers with acatalyst system according to any of paragraphs 1 to 5.7. Use of a compound of formula (1) as defined in any of paragraphs 1 to5 as activator of a transition metal compound in a catalyst system forthe polymerization of one or more olefins.8. A process for polymerizing one or more olefins, comprising contactingunder polymerization conditions one or more olefin monomers with acatalyst system comprising a transition metal compound and an activatorhaving the following formula (2):

[R_(n)AH]⁺ [Y]⁻,   (2)

wherein [Y]⁻ is a non-coordinating anion (NCA),A is nitrogen, phosphorus or oxygen,n is 3 if A is nitrogen or phosphorus, and n is 2 if A is oxygen,and the groups R are identical or different and are a C₁ to C₃ alkylgroup,wherein at a given reaction temperature the weight average molecularweight (Mw) of the polymer formed increases or at least does notsubstantially decrease with increasing monomer conversion.9. The process of any of paragraphs 6 or 8, or the use of paragraph 7,wherein the one or more olefins are alpha-olefins, and preferablypropylene, optionally in combination with another alpha-olefin.10. The process of any of paragraphs 6, 8 or 9, or the use of any ofparagraphs 7 or 9, wherein the activator is a combination of at leasttwo different compounds of formula (1) as defined in any of paragraphs 1to 5 and/or formula (2) as defined in paragraph 8.11. The process of any of claims 6, 8 or 9, or the use of any of claims7 or 9, wherein [R_(n)AH]⁺ is trimethylammonium, and [Y]⁻ istetrakis(pentafluorophenyl)borate, tetrakis(heptafluoronaphthyl)borateor tetrakis (perfluorobiphenyl)borate.12. The process or use of paragraph 11, wherein the transition metalcompound is a metallocene selected from the group consisting of arac-dimethylgermylbis(indenyl)halhocene or -zirconocene, arac-dimethylsilyl bis(indenyl) hafnocene or -zirconocene, arac-dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-indenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-4-naphthylindenyl)hafnocene or -zirconocene, or an ethylenyl bis(indenyl) hafnocene or-zirconocene, wherein the hafnocene and zirconocene has at least twoleaving groups X₁ and X₂ which are as defined in paragraph 4.13. The process of any of paragraphs 6, 8, 9, 10, 11, or 12, or the useof any of claims 7, 9, 10, 11, or 12, wherein the polymerization isconducted in solution and at a temperature of at least about 80° C.,preferably of at least about 100° C., more preferably of at least about120° C.14. The process of any of paragraphs 6, 8, 9, 10, 11, 12, or 13, or theuse of any of claims 7, 9, 10, 11, 12, or 13 wherein the monomerconversion is from 5 to 50%, preferably 5 to 98%.15. A polymer obtainable by a process according to paragraph 6 or any ofparagraphs 8 to 14.

EXAMPLES Polymer Characterizations GPC Method “C”—Gel PermeationChromatography—Alliance 2000 DRI Only

This method used a Waters Alliance 2000 gel permeation chromatographequipped with a Waters differential refractometer that measures thedifference between the refractive index of the solvent and that of thesolvent containing the fractionated polymer. The system was used at 145°C. with 1,2,4-Trichlorobenzene (TCB) as the mobile phase that wasstabilized with ˜250 ppm of butylated hydroxy toluene (BHT). The flowrate used was 1.0 mL/min. Three (Polymer Laboratories) PLgel Mixed-Bcolumns were used. This technique is discussed in “Macromolecules, Vol.34, No. 19, pp. 6812-6820” which is incorporated herein by reference.

The separation efficiency of the column set was calibrated using aseries of narrow molecular weight distribution polystyrene standards,which reflects the expected molecular weight range for samples and theexclusion limits of the column set. At least 10 individual polystyrenestandards, ranging from Mp ˜580 to 10,000,000, were used to generate thecalibration curve. The polystyrene standards were obtained from PolymerLaboratories (Amherst, Mass.) or an equivalent source. To assureinternal consistency, the flow rate was corrected for each calibrant runto give a common peak position for the flow rate marker (taken to be thepositive inject peak) before determining the retention volume for eachpolystyrene standard. The flow marker peak position thus assigned wasalso used to correct the flow rate when analyzing samples; therefore, itis an essential part of the calibration procedure. A calibration curve(log Mp vs. retention volume) was generated by recording the retentionvolume at the peak in the DRI signal for each PS standard, and fittingthis data set to a second order polynomial. Polystyrene standards weregraphed using Viscotec 3.0 software. Samples were analyzed usingWaveMetrics, Inc. IGOR Pro and Viscotec 3.0 software using updatedcalibration constants.

Differential Scanning Calorimetry

Peak melting point (Tm) and peak crystallization temperature (Tc), glasstransition temperature (Tg), and heat of fusion (ΔH) were determinedusing the following procedure according to ASTM D3418-03. Differentialscanning calorimetric (DSC) data were obtained using a TA Instrumentsmodel Q100 machine. Samples weighing approximately 5-10 mg were sealedin an aluminum hermetic sample pan. The DSC data were recorded by firstgradually heating the sample to 200° C. at a rate of 10° C./minute. Thesample was kept at 200° C. for 5 minutes then cooled down to −90° C. ata rate of 10° C./minute before a second cooling-heating cycle wasapplied. Both the first and second cycle thermal events were recorded.Areas under the endothermic peaks were measured and used to determinethe heat of fusion. The melting and crystallization temperaturesreported here were obtained during the second heating/cooling cycle.

Comonomer Content

The ethylene content of ethylene/propylene copolymers was determinedusing FTIR according to the following technique. A thin homogeneous filmof polymer, pressed at a temperature of about 150° C., was mounted on aPerkin Elmer Spectrum 2000 infrared spectrophotometer. A full spectrumof the sample from 600 cm⁻¹ to 4000 cm⁻¹ was recorded and the area underthe propylene band at ˜1165 cm⁻¹ and the area under the ethylene band at˜732 cm⁻¹ in the spectrum were calculated. The baseline integrationrange for the methylene rocking band is nominally from 695 cm⁻¹ to theminimum between 745 and 775 cm⁻¹. For the polypropylene band thebaseline and integration range is nominally from 1195 to 1126 cm⁻¹. Theethylene content in wt. % was calculated according to the followingequation:

ethylene content (wt. %)=72.698−86.495X+13.696X²

where X=AR/(AR+1) and AR is the ratio of the area for the peak at ˜1165cm⁻¹ to the area of the peak at ˜732 cm⁻¹.

Viscosity

Viscosity was measured using a Brookfield digital viscometer and anumber 27 spindle according to ASTM D-3236.

Proton NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹Hydrogen frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45° C., 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons. Mn was calculated by dividing thetotal number of unsaturated species into 14,000.

The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene 4.70-4.84 2 Vinylene 5.31-5.55 2 Trisubstituted5.11-5.30 1

Catalyst Synthesis

Synthetic procedures involving air-sensitive compounds were performed ina Vacuum Atmospheres drybox maintained under a N₂ atmosphere. Anhydroussolvents were purchased from Aldrich and dried over 2 Å sieves. Me₃NHCland N-Methylpyrrolidine were purchased from Aldrich. Me₂Si(C₉H₆)₂HfMe₂and C₂H₄(C₉H₆)₂ZrMe₂ were purchased from Boulder Scientific.Me₂Ge(C₉H₆)₂HfMe₂ was synthesized as disclosed in the art.[Ph₃C][B(C₆F₅)₄, [PhNMe₂H][B(C₁₀F₇)₄] and [Na][B(C₁₀F₇)₄] were purchasedfrom Grace Davison. [nBu₃NH][B(C₆F₅)₄] and [PhNMe₂H][B(C₆F₅)₄] werepurchased from Albemarle. The individual syntheses of activators used inthe examples are described in the following:

Trimethylammonium tetrakis(pentafluorophenyl)borate

LiB(C₆F₅)₄.Et₂O (3.3 g, 4.3 mmol) was dissolved in 100 ml CH₂Cl₂ atambient temperature. Solid Me₃NHCl (0.41 g, 4.3 mmol) was added to thereaction mixture in portions over 10 minutes. The reaction mixture wasstirred for 15 hours and was filtered through a glass frit with Celiteto remove LiCl. The colorless filtrate was reduced in vacuo to a whitesolid. The product was dried in vacuo for 1 hour at 50° C. to yield 2.7g of product. ¹H NMR (CCl₂D₂) δ ppm: 6.4 (br s, 1H), 2.97 (d, 9H).

Trimethylammonium tetrakis(heptafluoro-2-naphthyl)borate

NaB(2-C₁₀F₇)₄ (2.2 g, 2.1 mmol) was dissolved in 100 ml CH₂Cl₂ andreacted with Me₃NHCl (0.20 g, 2.1 mmol) for 2 hours at ambienttemperature. The reaction mixture was filtered over a glass frit and thelight yellow filtrate reduced in vacuo. The product was dried in vacuofor 12 hours to yield a light tan solid (1.6 g). ¹H NMR (CCl₂D₂) δ ppm:8.1 (very br s, 1H), 2.85 (d, 9H).

N-Methylpyrrolidinium tetrakis(pentafluorophenyl)borate

N-Methylpyrrolidinium hydrochloride was prepared from the respectiveamine by hydrochlorination using HCl (2 M, Et₂O) in pentane. Theresulting solid product was filtered and dried in vacuo.N-methylpyrrolidine. HCl (0.35 g, 2.9 mmol) was dissolved in 150 mldichloromethane at room temperature. Solid LiB(C₆F₅)₄.Et₂O (2.2 g, 2.86mmol) was added to the reaction mixture in portions over 10 minutes.After 2 hours the reaction mixture was filtered through a glass frit toremove LiCl and the colorless filtrate reduced in vacuo to yield a whitesolid. The product was dried in vacuo for 12 hours to yield 1.9 g ofproduct. ¹H NMR (CCl₂D₂) δ ppm: 7.55 (br s, 1 H), 3.70 (m, 2 H), 2.95(m, 2 H), 4.82 (d, 3 H). 2.0 to 2.25 (m, 4 H).

N-Methylpyrrolidinium tetrakis(heptafluoro-2-naphthyl)borate

N-methylpyrrolidinium hydrochloride (0.50 g, 4.1 mmol) was dissolved in100 ml dichloromethane at room temperature. Solid NaB(2-C₁₀F₇)₄ (4.3 g,4.1 mmol) was added to the reaction mixture in portions over 10 minutes.After 1 hour the reaction mixture was allowed to settle for anadditional hour and then filtered through a glass frit to remove NaCl.The light amber-colored filtrate was reduced in vacuo to yield a tansolid. The product was dried in vacuo an additional hour at 50° C. andthe final yield was 4.3 g.

¹H NMR (C₆D₆) δ ppm: 8.6 (br s, 1 H), 2.35-2.5 (m, 2 H), 1.57 (d, 3 H),1.3-1.5 (m, 2 H), 0.85-1.3 (m, 4 H).

Supported Catalyst Synthesis

rac-Dimethylsilylbis(indenyl)hafnium dimethyl/trimethylammoniumtetrakis(pentafluorophenyl)borate Supported on Silica

Ineos ES-757 silica gel, 20 g (calcined at 600° C.) was slurried in 100ml of toluene and reacted with 38 g triethylaluminum (25 wt % intoluene). The mixture was stirred for 12 to 15 hours at ambienttemperature. Solid was collected on a glass frit, washed with hexane anddried in vacuo. The modified support was obtained as a whitefree-flowing solid (21.8 g). The modified ES-757 (2.0 g) was slurried intoluene (30 ml) and reacted with Activator 4 (107 mg) for 30 min.Metallocene A (72 mg) was added and allowed to react for 2 hours. Thesupported catalyst was isolated on a glass frit, washed with toluene (30mLs) and dried in vacuo to yield 1.96 g supported catalyst.

Polymerization Example 1 (see FIG. 1) Batch Polymerization of Propylene

TIBAL (triisobutylaluminum, Aldrich) (0.4 mL, 1.0 M in hexane) was addedto a 1 L autoclave followed by 500 mL isohexanes at room temperatureunder N₂ purge. Propylene was then added by volume as measured from asight glass with increments of 10 mLs. The autoclave was heated totemperature, allowed to stabilize and the total reaction pressurerecorded. The catalyst system was added as a pre-activated solution ofmetallocene and activator in toluene solution via catalyst tube withhigh pressure N₂ flush. The flush was repeated 2 times. Afterpolymerization was complete, the autoclave contents were cooled to roomtemperature and the excess pressure safely vented. The contents weretransferred into a glass container and volatiles were removed by a N₂purge. The polymer was dried in a vacuum oven at 70° C. for 2 to 3hours.

The metallocenes and activators used in the batch experiments of Example1 in various combinations are abbreviated as follows (activators thatare not according to the present invention are marked with a star*):

Metallocenes: rac-dimethylsilylbis(indenyl)hafnium dimethyl Arac-ethylenylbis(indenyl)zirconium dimethyl Brac-dimethylgermylbis(indenyl)hafnium dimethyl C Activators:Dimethylanilinium tetrakis(pentafluorophenyl)borate*,[PhNMe₂H]⁺[B(C₆F₅)₄]⁻ 1* Trityl tetrakis(pentafluorophenyl)borate*,[(C₆H₅)₃C]⁺ [B(C₆F₅)₄]⁻ 2* Tri(n)butylammoniumtetrakis(pentafluorophenyl)borate*, [nBu₃NH]⁺ [B(C₆F₅)₄]⁻ 3*Trimethylammonium tetrakis(pentafluorophenyl)borate, [Me₃NH]⁺[B(C₆F₅)₄]⁻ 4 N-methylpyrrolidinium tetrakis(pentafluorophenyl)borate[MePyrH]⁺ [B(C₆F₅)₄]⁻ 5 [H(OEt)₂]⁺[B(C₆F₅)₄]⁻ 6 Dimethylaniliniumtetrakis(heptafluoronaphthyl)borate*, [PhNMe₂H]⁺ [B(C₁₀F₇)₄]⁻ 7*Trimethylammonium tetrakis(heptafluoronaphthyl)borate, [Me₃NH]⁺[B(C₁₀F₇)₄]⁻ 8 N-methylpyrrolidiniumtetrakis(heptafluoronaphthyl)borate, [MePyrH]⁺ [B(C₁₀F₇)₄]⁻ 9

The results of the batch polymerization runs are given below in Tables1a, 1b, 2a, 2b and 3. FIG. 1 shows the results given in Tables 1a and1b, in particular:

-   Run 1 (comparative): A-1-   Run 2 (comparative): A-2-   Run 3 (comparative): A-3-   Run 4: A-4-   Run 5: A-5

TABLE 1a Activity Run Run Metal Metal gPP/ Propylene, temp time Polymercompl. complex Metal mmol Metallocene Activator mLs ° C. min yield g mgMw mmol metal. A 1 100 120 10 11.8 3.3 495.0 0.00667 1770.0 A 1 100 12020 11.3 6.6 495.0 0.01333 847.5 A 1 100 120 20 19.3 6.6 495.0 0.013331447.5 A 2 100 120 20 3.85 6.6 495.0 0.01333 288.8 A 2 100 120 20 11.56.6 495.0 0.01333 862.5 A 3 100 120 20 5.4 6.6 495.0 0.01333 405.0 A 3100 120 20 11.6 6.6 495.0 0.01333 870.0 A 4 100 120 20 4.6 6.6 495.00.01333 345.0 A 4 100 120 20 13.1 6.6 495.0 0.01333 982.5 A 5 100 120 206.6 3.3 495.0 0.00667 990.0 A 5 100 120 20 4.4 3.3 495.0 0.00667 660.0

TABLE 1b T_(m) Mw Mn Mw/ (DSC) Δ H, Metallocene Activator (g/mol)(g/mol) Mn vinylenes tri-sub vinyls vinylidenes ° C. J/g Conv. % A 17,508 3,943 1.9 0.07 0.06 1.58 1.89 70.8 23.4 A 1 8,169 3,451 2.37 0.10.11 1.49 1.99 81.7 27.7 22.4 A 1 5,398 2,323 2.32 0.12 0.14 2.28 2.6884.02 16.6 38.2 A 2 10,175 4,648 2.19 0.12 0.29 1.21 1.55 98.1 39.8 7.6A 2 7,881 3,781 2.08 0.1 0.27 1.66 1.93 76.34 22.8 A 3 9,686 4,376 2.210.12 0.02 1.14 1.9 94.7 35 10.7 A 3 7,571 3,345 2.26 0.14 0.09 1.44 2.0174.9 23.0 A 4 9,352 4,037 2.32 0.14 0.08 1.18 1.94 93.4 36.4 9.1 A 410,867 4,775 2.28 0.08 0.14 1.13 1.71 100.6 40.6 25.9 A 5 15459 7067 2.20.08 0.05 1.07 1.15 104.2 60.3 13.1 A 5 13520 6670 2 0.13 0.12 1.03 1.42102.3 59.8 8.7

TABLE 2a Run Run Metal Metal Activity Propylene, temp, time, Polymercompl. complex Metal gPP/mmol Metallocene Activator mLs ° C. min yield,g mg Mw mmol Metal. A 6 100 120 20 1.3 8.0 495.0 0.01616 80.4 A 6 100120 20 6.33 8.0 495.0 0.01616 391.7 A 7 100 120 20 10.36 3.3 495.00.00673 1540.0 A 7 100 120 20 8.05 3.3 495.0 0.00673 1196.6 A 8 100 12020 11.44 3.3 495.0 0.00673 1700.5 A 8 100 120 20 3.84 3.3 495.0 0.00673570.8 A 9 100 120 20 7.38 3.3 495.0 0.00673 1097.0 A 9 100 120 20 4.553.3 495.0 0.00673 676.4 A 7 200 120 20 3.64 3.3 495.0 0.00673 541.1 A 7200 120 20 35.1 3.3 495.0 0.00673 5217.6 A 8 200 120 20 14.83 3.3 495.00.00673 2204.5 A 8 200 120 20 19.75 3.3 495.0 0.00673 2935.8 A 8 200 12020 26.81 3.3 495.0 0.00673 3985.3 A 8 200 120 20 25.51 3.3 495.0 0.006733792.0 B 8 100 120 20 42.94 2.3 377.2 0.00610 7042.2 B 8 100 120 2049.94 2.3 377.2 0.00610 8190.2 C 1 100 120 20 7.02 3.6 539.3 0.006681051.6 C 1 100 120 20 2.93 3.6 539.3 0.00668 438.9 C 4 100 120 20 3.143.6 539.3 0.00668 470.4 C 4 100 120 20 4.46 3.6 539.3 0.00668 668.1

TABLE 2b T_(m) Mw Mn Mw/ (DSC) Δ H Metallocene Activator (g/mol) (g/mol)Mn vinylenes tri-sub vinyls vinylidenes ° C. J/g Conv. % A 6 10,0561,205 8.34 0.17 0.15 1.49 3.4 97.8 38.3 2.6 A 6 8,460 1,665 5.08 0.170.13 1.49 2.9 91.6 37.2 12.5 A 7 16,571 5593 2.96 0 0.03 0.87 0.26 93.345.3 20.5 114.4 A 7 20,807 7,192 2.89 0.07 0.11 1.63 0.35 103.5 49.515.9 115.7 A 8 20,795 7,628 2.73 0.04 0.08 0.99 0.41 57.2 44.7 22.7 96.1110.1 A 8 20,947 7,629 2.78 0.04 0.01 0.77 0.46 58.7 43.2 7.6 87.2 A 927408 14263 1.92 0.02 0.07 1.05 0.39 105.1 59.5 14.6 A 9 28807 157011.83 0.04 0.07 0.69 0.34 114.5 52.9 9.0 A 7 39768 19095 2.1 0.06 0.10.52 0.47 18.1 57.9 3.6 103.9 116.4 A 7 16555 5877 2.82 0.08 0.2 2.260.34 89.9 47.9 34.8 103.8 126.4 136.2 A 8 29,540 14898 2 0.05 0.06 0.980.35 30.1 60.2 14.7 63.5 112.7 137.9 A 8 28021 12514 2.2 0.03 0.08 1.740.41 53.1 55.8 19.6 64.6 92.4 109.4 147.7 A 8 33364 16443 2.03 0.06 0.080.8 0.27 111.4 67 26.5 A 8 35071 15949 2.2 0.04 0.08 0.55 0.19 37.5 60.425.3 49.2 91.4 111.9 B 8 5052 1305 3.87 0.26 0.35 1.05 3.74 85.0 B 85527 1243 4.4 0.26 0.31 1.01 3.56 98.9 C 1 7100 2274 3.12 0.07 0.05 1.942.6 104.1 55.2 13.9 C 1 8789 2634 3.34 0.02 0.01 1.92 2.91 94.4 50.7 5.8C 4 9028 3715 2.43 0.14 0.04 1.61 2.11 101.8 55.1 6.2 C 4 9889 4282 2.310.13 0.1 1.39 1.75 103.1 60.8 8.8

TABLE 3 (supported catalyst system - slurry polymerization): ActivityRXR Product Cat. C2 = psig Cat (g) Tp. (C) Time (hr) Yield (g) g/g/hrL105 PE A-4/ 300 0.1 80 1 107 1070 teal757 DSC GPC-DRI (g/mol) Tg, ° C.Tm, ° C. ΔH (J/g) Tc, ° C. Mn Mw Mz Mw/Mn 135.7 152.0 115.0 152,578543,685 1,228,140 3.56 ¹H NMR - (Unsat./1000 C.) vinylenes olefinsvinyls vinylidenes 0.06 0.05 0.08 0.03

For following examples 2-4, the following characterization procedure wasused. (For purposes of the claims the following GPC procedure shall beused.)

Molecular weights (number average molecular weight (Mn), weight averagemolecular weight (Mw), and z-average molecular weight (Mz)) and g′viswere determined using a Polymer Laboratories Model 220 high temperatureSEC with on-line differential refractive index (DRI), light scattering,and viscometer detectors. It used three Polymer Laboratories PLgel 10 mMixed-B columns for separation, a flow rate of 0.54 cm³/min, and anominal injection volume of 300 μL. The detectors and columns arecontained in an oven maintained at 135° C. The light scattering detectoris a high temperature miniDAWN (Wyatt Technology, Inc.). The primarycomponents are an optical flow cell, a 30 mW, 690 nm laser diode lightsource, and an array of three photodiodes placed at collection angles of45°, 90°, and 135°. The stream emerging from the SEC columns is directedinto the miniDAWN optical flow cell and then into the DRI detector. TheDRI detector is an integral part of the Polymer Laboratories SEC. Theviscometer is a high temperature viscometer purchased from ViscotekCorporation and comprising four capillaries arranged in a Wheatstonebridge configuration with two pressure transducers. One transducermeasures the total pressure drop across the detector, and the other,positioned between the two sides of the bridge, measures a differentialpressure. The viscometer is inside the SEC oven, positioned after theDRI detector. The details of these detectors as well as theircalibrations have been described by, for example, T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, in Macromolecules, Volume 34, Number 19,6812-6820, (2001), incorporated herein by reference.

Solvent for the SEC experiment was prepared by adding 6 grams ofbutylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of1,2,4 trichlorobenzene (TCB) (Aldrich Reagent grade) and waiting for theBHT to solubilize. The TCB mixture was then filtered through a 0.7micron glass pre-filter and subsequently through a 0.1 micron Teflonfilter. There was an additional online 0.7 micron glass pre-filter/0.22micron Teflon filter assembly between the high pressure pump and SECcolumns. The TCB was then degassed with an online degasser (Phenomenex,Model DG-4000) before entering the SEC. Polymer solutions were preparedby placing dry polymer in a glass container, adding the desired amountof TCB, then heating the mixture at 160° C. with continuous agitationfor about 2 hours. All quantities were measured gravimetrically. The TCBdensities used to express the polymer concentration in mass/volume unitswere 1.463 g/ml at room temperature and 1.324 g/ml at 135° C. Theinjection concentration ranged from 1.0 to 2.0 mg/ml, with lowerconcentrations being used for higher molecular weight samples.

Branching index in these examples was measured using SEC with an on-lineviscometer (SEC-VIS) and is reported as g′ at each molecular weight inthe SEC trace. The branching index g′ is defined as:

$g^{\prime} = \frac{\eta_{b}}{\eta_{l}}$

where η_(b) is the intrinsic viscosity of the branched polymer and η_(l)is the intrinsic viscosity of a linear polymer of the sameviscosity-averaged molecular weight (M_(v)) as the branched polymer.η_(l)=KM_(v) ^(α), K and α were measured values for linear polymers andshould be obtained on the same SEC-DRI-LS-VIS instrument as the one usedfor branching index measurement. For polypropylene samples in theseexamples, K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VIS methodobviates the need to correct for polydispersities, since the intrinsicviscosity and the molecular weight were measured at individual elutionvolumes, which arguably contain narrowly dispersed polymer. Linearpolymers selected as standards for comparison should be of the sameviscosity average molecular weight, monomer content and compositiondistribution. Linear character for polymer containing C2 to C10 monomersis confirmed by Carbon-13 NMR using the method of Randall (Rev.Macromol. Chem. Phys., C29 (2&3), p. 285-297). Linear character for C11and above monomers is confirmed by GPC analysis using a MALLS detector.For example, for a copolymer of propylene, the NMR should not indicatebranching greater than that of the co-monomer (i.e. if the comonomer isbutene, branches of greater than two carbons should not be present). Fora homopolymer of propylene, the GPC should not show branches of morethan one carbon atom. When a linear standard is desired for a polymerwhere the comonomer is C9 or more, one can refer to T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) for protocols on determining standards for thosepolymers. In the case of syndiotactic polymers, the standard should havea comparable amount of syndiotacticity as measured by Carbon 13 NMR. Theviscosity averaged g′ was calculated using the following equation:

$g_{vis}^{\prime} = \frac{\sum{C_{i}\left\lbrack \eta_{i} \right\rbrack}_{b}}{\sum{C_{i}{KM}_{i}^{\alpha}}}$

where C_(i) is the polymer concentration in the slice i in the polymerpeak, and [η_(i)]_(b) is the viscosity of the branched polymer in slicei of the polymer peak, and M_(i) is the weight averaged molecular weightin slice i of the polymer peak measured by light scattering, K and α areas defined above.

Polymerization Example 2 (see FIGS. 2 a, 2 b) Continuous Polymerizationof Propylene

General polymerization procedure in a continuous stirred-tank reactor:all polymerizations were performed in a liquid filled, single-stagecontinuous reactor system. The reactor was a 0.5-liter stainless steelautoclave reactor and was equipped with a stirrer, a water cooling/steamheating element with a temperature controller, and a pressurecontroller. Solvents, propylene, and comonomers were first purified bypassing through a three-column purification system. The purificationsystem consisted of an Oxiclear column (Model # RGP-R1-500 fromLabclear) followed by a 5A and a 3A molecular sieve column. Purificationcolumns were regenerated periodically whenever there was evidence oflower activity of polymerization. Both the 3A and 5A molecular sievecolumns were regenerated in-house under nitrogen at a set temperature of260° C. and 315° C., respectively. The molecular sieve material waspurchased from Aldrich. Oxiclear column was regenerated in the originalmanufacture. Ethylene was delivered as a gas solubilized in the chilledsolvent/monomer mixture. The purified solvents and monomers were thenchilled to about −15° C. by passing through a chiller before being fedinto the reactor through a manifold. Solvent and monomers were mixed inthe manifold and fed into reactor through a single tube. All liquid flowrates were measured using Brooksfield mass flow meters or Micro-MotionCoriolis-type flow meters.

The metallocenes were pre-activated with an activator (of formula (1) or(2) according to the present invention or a comparative activator) at amolar ratio of about 1:1 in toluene. The preactivated catalyst solutionwas kept in an inert atmosphere with <1.5 ppm water content and was fedinto reactor by a metering pump through a separated line. Catalyst andmonomer contacts took place in the reactor.

As an impurity scavenger, 250 ml of tri-n-octyl aluminum (TNOA) (25 wt %in hexane, Sigma Aldrich) was diluted in 22.83 kilogram of isohexane.The TNOA solution was stored in a 37.9-liter cylinder under nitrogenblanket. The solution was used for all polymerization runs until about90% of consumption, and then a new batch was prepared. The feed rates ofthe TNOA solution were adjusted in a range from 0 (no scavenger) to 4 mlper minute to achieve a maximum catalyst activity.

The reactor was first prepared by continuously N₂ purging at a maximumallowed temperature, then pumping isohexane and scavenger solutionthrough the reactor system for at least one hour. Monomers and catalystsolutions were then fed into the reactor for polymerization. Once theactivity was established and the system reached equilibrium, the reactorwas lined out by continuing operation of the system under theestablished condition for a time period of at least five times of meanresidence time prior to sample collection. The resulting mixture,containing mostly solvent, polymer and unreacted monomers, was collectedin a collection box. The collected samples were first air-dried in ahood to evaporate most of the solvent, and then dried in a vacuum ovenat a temperature of about 90° C. for about 12 hours. The vacuum ovendried samples were weighed to obtain yields. All the reactions werecarried out at a pressure of about 2 MPa.

Example 2 demonstrates the polymerization of propylene usingrac-dimethylsilylbis(indenyl)hafnium dimethyl, see FIGS. 2 a and 2 b.The metallocene was pre-activated with an activator at a molar ratio ofabout 1:1 in toluene: The activators used were (1) N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (comparative, obtained fromAlbemarle), (2) Me₃NH tetrakis(pentafluorophenyl)borate and (3) Me₃NHtetrakis(heptafluoro-2-naphthyl) borate. The detailed polymerizationconditions and some of analytical data for materials produced in thesepolymerization examples are listed in Tables 4a to 4c. For all thepolymerizations, isohexane feed rate was 80 ml/min, propylene feed ratewas 14 g/min. Polymerization examples listed in Tables 4c arecomparative.

TABLE 4a Polymerization of propylene usingdimethylsilylbis(indenyl)hafnium dimethyl/Me₃NHtetrakis(pentafluorophenyl)borate Example # 2-1 2-2 2-3 2-4 2-5Polymerization temperature (° C.) 120 110 100 90 80 Metallocene feedrate (mol/min) 4.5E−07 4.5E−07 4.5E−07 4.5E−07 4.5E−07 Conversion (%)66.8 67 65 55.1 37.9 Mn (kg/mol) 10.49 14.85 22.19 39.01 63.83 Mw(kg/mol) 25.24 32.70 47.32 74.32 121.36 Mz (kg/mol) 43.73 54.21 76.35114.60 190.33 g'vis 0.95 0.95 0.97 0.98 1.01 Tc (° C.) 70.2 79.0 86.790.8 95.6 Tm (° C.) 104.9 113.9 122.6 128.8 133.4 Tg (° C.) −12.2 −8.4−8.5 Heat of fusion (J/g) 51.6 69.0 71.8 84.3 88.2 Viscosity @ 190° C.(mPa · s) 534 1090 4210 24500 128300 Catalyst activity (kg polymer/gmetallocene) 42.09 42.21 40.95 34.72 23.88

TABLE 4b Propylene polymerization using dimethylsilylbis(indenyl)hafniumdimethyl/Me₃HN tetrakis(heptafluoro-2-naphthyl) borate Example # 2-6 2-72-8 2-9 2-10 Polymerization temperature (° C.) 120 110 100 90 80Metallocene feed rate (mol/min) 6.1E−07 6.1E−07 6.1E−07 6.1E−07 6.1E−07Conversion (%) 80.8 80.3 83.2 67.8 34.5 Mn (kg/mol) 10.01 15.75 20.6625.36 28.46 Mw (kg/mol) 29.22 48.21 51.61 95.14 147.79 Mz (kg/mol) 54.5891.20 94.39 173.59 272.41 g'vis 0.88 0.91 0.93 1.00 1.03 Tc (° C.) 53.172.0 77.7 92.8 98.1 Tm (° C.) 96.9 111.2 116.2 130.2 137.6 Tg (° C.)−10.4 −8.9 −8.9 Heat of fusion (J/g) 43.6 58.5 65.5 78.1 82.3 Viscosity@ 190° C. (mPa · s) 805 4105 5516 74830 345000 Catalyst activity (kgpolymer/g metallocene) 37.70 37.47 38.82 31.64 16.10

TABLE 4c Propylene polymerization using dimethylsilylbis(indenyl)hafniumdimethyl/N,N- dimethylanilinium tetrakis(pentafluorophenyl)borate(comparative) Example # 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18Polymerization temperature 130 120 110 100 90 80 70 60 (° C.)Metallocene feed rate 1.9E−06 1.9E−06 1.9E−06 1.9E−06 1.9E−06 1.9E−061.9E−06 1.9E−06 (mol/min) Conversion (%) 73.9 81.8 88.1 85.6 86.1 89.4108.6 89.9 Mn (kg/mol) 3.12 6.13 15.59 37.87 Mw (kg/mol) 10.25 16.3532.35 79.08 Mz (kg/mol) 153.99 28.41 52.22 132.39 g'vis 1.09 0.95 0.930.95 Tc (° C.) 32.3 39.9 49.3 59.6 68.4 81.6 91.7 97.8 Tm (° C.) 69.080.4 90.3 99.4 107.8 118.0 127.6 131.3 Tg (° C.) −26.8 −17.6 −19.5 −11.7−8.2 Heat of fusion (J/g) 19.6 23.6 35.6 44.5 56.5 61.2 67.7 73.3Viscosity @ 190° C. (mPa · s) 43.1 85.3 131 311 877 3660 31100 Catalystactivity 10.95 12.13 13.05 12.68 12.75 13.24 16.08 13.31 (kg polymer/ gmetallocene)

Polymerization Example 3 (see FIGS. 3 a, 3 b) Continuous Polymerizationof Propylene

Example 3 demonstrates the polymerization of propylene usingrac-dimethylsilylbis(indenyl) zirconium dimethyl, see FIGS. 3 a and 3 b.The metallocene was pre-activated with Me₃NHtetrakis(heptafluoro-2-naphthyl) borate at a molar ratio of about 1:1 intoluene. The same general polymerization procedure described above inExample 2 was used, and detailed polymerization conditions and some ofthe analytical data for materials produced in these polymerizationexamples are listed in Table 5a. For all the polymerization runs,isohexane feed rate was 80 ml/min, propylene feed rate was 14 g/min, andthe metallocene feed rate was 7.835E-07 mole/min. As comparativeexamples, Table 5b lists the polymerization conditions and somecharacterization data for polypropylene produced usingrac-dimethylsilylbis(indenyl) zirconium dimethyl preactived withdimethylanilinium tetrakis(heptafluoronaphthyl) borate at a molar ratioof about 1:1 in toluene.

TABLE 5a Propylene polymerization using rac-dimethylsilylbis(indenyl)zirconium dimethyl/Me₃NH tetrakis(heptafluoro-2-naphthyl) borate Example# 3-1 3-2 3-3 3-4 3-5 Polymerization 120 110 100 90 80 temperature (°C.) Conversion (%) 88.1 82.1 77.4 64.3 58.8 Tc (° C.) 51.0 57.7 77.189.8 96.3 Tm (° C.) 77.1 97.2 113.7 124.7 132.6 Tg (° C.) −18.6 −13.9−10.9 Heat of fusion (J/g) 21.9 47.6 60.6 79.8 85.5 Viscosity @190 C(cp) 65 167.5 360 705 1257 Catalyst activity (kg 38.61 35.98 33.92 28.1825.77 polymer/g metallocene)

TABLE 5b Propylene polymerization using rac-dimethylsilylbis(indenyl)zirconium dimethyl/ dimethylanilinium tetrakis(heptafluoronaphthyl)borate (comparative) Polymerization temperature (° C.) 120 110 100 90 80Cat (mol/min) 7.835E−07 7.835E−07 7.835E−07 7.835E−07 7.835E−07Propylene (g/min) 14 14 14 14 14 Yield (g/min) 11.1 11.1 11.1 11.1 10.9Conversion (%) 79.3 79.4 79.1 79.2 77.9 Tc (° C.) 25.3 44.6 68.6 83.891.9 Tm (° C.) 69.9 89.8 106.4 119.1 128.0 Tg (° C.) −20.4 −14.7 −12.8Heat of fusion (J/g) 26.3 42.1 56.5 69.9 81.7 Viscosity @ 190 C (mPa ·s) 41.7 103 245 538 1120 Catalyst activity (kg polymer/g metallocene)34.75 34.80 34.66 34.71 34.14

Polymerization Example 4 Continuous Polymerization of Ethylene/Propylene

Example 4 demonstrates the polymerization of ethylene/propylenecopolymer using rac-dimethylsilylbis(indenyl) hafnium dimethylpre-activated with a trimethylammonium tetrakis(pentafluorophenyl)borateat a molar ratio of about 1:1 in toluene. The polymerization runs weregenerally carried out according to the procedure described above forExample 2.

TABLE 6 Polymerization of ethylene/propylene copolymers usingrac-dimethylsilylbis(indenyl) hafnium dimethyl/trimethylammoniumtetrakis(pentafluorophenyl)borate Example # 4-1 4-2 4-3 4-4 4-5 4-6Polymerization temperature (° C.) 90 90 90 90 90 90 Propylene feed rate(g/min) 14 14 14 14 14 14 Ethylene feed rate (SLPM) 0.5 0.7 0.9 1.2 1.52 Isohexane feed rate (ml/min) 80 80 80 80 80 80 Metallocene feed rate(mol/min) 2.7E−07 2.7E−07 2.7E−07 2.7E−07 2.7E−07 2.7E−07 Conversion (%)44.1 48.3 52 45.3 46.1 45.8 Mn(kg/mol) 29.733 23.03 30.009 19.579 15.84825.868 Mw (kg/mol) 92.85 87.915 88.199 86.887 81.576 88.374 Mz (kg/mol)157.77 153.426 150.387 150.825 148.804 152.828 Mw/Mn 3.12 3.82 2.94 4.445.15 3.42 g'vis 0.957 0.961 0.959 0.98 0.886 0.941 Tc (° C.) 31.46 14.5211.05 Tm (° C.) 79.27 68.97 59.44 Tg (° C.) −22.07 −24.1 −26.65 −29.24−32.02 −31.38 Heat of fusion (J/g) 36.05 27.15 13.05 Ethylene content(wt %) 12.35 12.7 15.24 20.51 27.51 20.7 Viscosity @190° C. (mPa · s)166000 140000 140000 170000 184000 260000 SLPM = standard liter perminute.

Polymerization Example 5 Continuous Polymerization of Propylene

Example 5 demonstrates the polymerization of propylene usingrac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl. Themetallocene was pre-activated with Me₃NH tetrakis(pentafluorophenyl)borate at a molar ratio of about 1:1 in toluene. The same generalpolymerization procedure described above in Example 2 was used, anddetailed polymerization conditions and some of the analytical data formaterials produced in these polymerization examples are listed in Table7. For all the polymerization runs, isohexane was used a solvent and thefeed rate was 80 ml/min, propylene feed rate was 14 g/min, and themetallocene feed rate was 4.545E-07 mole/min.

TABLE 7 Polymerization of propylene using rac-dimethylsilylbis(2-methyl-4- phenylindenyl) zirconium dimethyl/Me₃NHtetrakis(pentafluorophenyl)borate Example # 5-1 5-2 5-3 5-4 5-5Polymerization 130 120 110 100 90 temperature (° C.) Conversion (%) 89.291 92 92.4 93.8 Mn (kg/mol) 3.9 5.6 8.5 12.2 16.2 Mw (kg/mol) 11.5 17.226.5 39.9 63.2 Mz (kg/mol) 22.0 33.0 50.2 77.6 135.8 g'vis 0.82 0.820.81 0.83 0.83 Tc (° C.) 84.3 91.6 99.4 103.7 107.4 Tm (° C.) 122.3129.5 137.3 143.2 149.1 Tg (C.) Heat of fusion (J/g) 76.7 83.0 90.4 95.4100.0 Viscosity @190° C. 93.9 185 504 1670 9750 (mPa · s) productivity(kg 46.83 47.78 48.30 48.51 49.25 polymer/g metallocene)

Additional batch propylene polymerizations were run according to theprocedure in Example 1, except that 100 mls of propylene were used, therun temperature was 120° C., and the run time was 20 minutes. The dataare reported in Table 7a and 7b.

TABLE 7a Metal Metal Activity, Activity, Polymer complex, complex MetalgPP/mmol gPP/mmolMet · mL Example MCN Act yield, g mg Mw mmol Met PP 7-1B 7 34.37 2.3 377.2 0.00610 5636.7 56.4 7-2 B 7 49.45 2.3 377.2 0.006108109.8 81.1 7-3 C 7 12.27 3.6 539.3 0.00668 1838.1 18.4 7-4 C 7 11.123.6 539.3 0.00668 1665.8 16.7

TABLE 7b Mw Mn ΔH, Conversion Ex (g/mol) (g/mol) Mw/Mn vinylenes trisubvinyls vinylidenes (J/g) (%) 7-1 4790 1098 4.4 0.32 0.36 1.03 4.19 68.17-2 4992 1157 4.31 0.26 0.31 1.02 3.82 97.9 7-3 17498 8052 2.2 0.01 0.011.69 0.39 64.5 24.3 7-4 17675 8609 2.1 0.03 0.08 1.48 0.32 72.5 22.0Melting point for the polymer in 7-5 was 108° C.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby.

1.-15. (canceled)
 16. A process for polymerizing one or more olefins,comprising contacting under polymerization conditions one or more olefinmonomers with a catalyst system comprising a transition metal compoundand an activator having the following formula (2):[R_(n)AH]⁺ [Y]⁻,   (2) wherein [Y]⁻ is a non-coordinating anion, A isnitrogen, phosphorus or oxygen, n is 3 if A is nitrogen or phosphorus,and n is 2 if A is oxygen, and the groups R are identical or differentand are a C₁ to C₃ alkyl group, wherein at a given reaction temperaturethe weight average molecular weight (Mw) of the polymer formed increasesor at least does not substantially decrease with increasing monomerconversion.
 17. The process of claim 16, wherein the one or more olefinsare alpha-olefins, optionally in combination with another alpha-olefin.18. The process of claim 16, wherein the one or more olefins comprisepropylene.
 19. The process of claim 16, wherein [R_(n)AH]⁺ istrimethylammonium, and [Y]⁻ is tetrakis(pentafluorophenyl)borate,tetrakis(heptafluoronaphthyl)borate or tetrakis(perfluorobiphenyl)borate.
 20. The process of claim 16, wherein thetransition metal compound is a metallocene selected from the groupconsisting of a rac-dimethylgermylbis(indenyl)hafnocene or -zirconocene,a rac-dimethylsilyl bis(indenyl) hafnocene or -zirconocene, arac-dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-indenyl) hafnocene or-zirconocene, a rac-dimethylsilyl bis(2-methyl-4-naphthylindenyl)hafnocene or -zirconocene, and an ethylenyl bis(indenyl) hafnocene or-zirconocene.
 21. The process of claim 16, wherein the polymerization isconducted in solution and at a temperature of at least about 80° C. 22.The process of claim 16 wherein the monomer conversion is from 5 to 50%.23. (canceled)
 24. The process of claim 16, wherein the activator is acombination of at least two different compounds of formula (2). 25.(canceled)
 26. The process of claim 16, wherein the transition metalcompound is represented by the following formula:

wherein M is zirconium or hafnium; n is 0 or 1; T is selected fromdialkylsilyl, diarylsilyl, dialkylmethyl, ethylenyl (—CH₂—CH₂—) orhydrocarbylethylenyl wherein one, two, three or four of the hydrogenatoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl canbe independently C₁ to C₁₆ alkyl or phenyl, tolyl, xylyl and the like,and when T is present, the catalyst represented can be in a racemic or ameso form; L₁ and L₂ are the same or different indenyl rings, that areeach bonded to M; X₁ and X₂ are, independently, hydrogen, halogen,hydride radicals, hydrocarbyl radicals, substituted hydrocarbylradicals, halocarbyl radicals, substituted halocarbyl radicals,silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbylradicals, or substituted germylcarbyl radicals; or both X are joined andbound to the metal atom to form a metallacycle ring containing fromabout 3 to about 20 carbon atoms; or both together can be an olefin,diolefin or aryne ligand.
 27. The process of claim 16, wherein thetransition metal compound is dimethylsilylbis(indenyl)hafnium dimethyl,rac-dimethylsilylbis(indenyl)zirconium dimethyl,rac-ethylenylbis(indenyl)zirconium dimethyl, orrac-ethylenylbis(indenyl)hafnium dimethyl.
 28. The process of claim 16,wherein the transition metal compound is a bridged or unbridgedbis(substituted or unsubstituted indenyl) hafnium dialkyl or dihalide.29. The process of claim 16, wherein the transition metal compound is adialkylsilylbis(indenyl) metallocene, wherein the metal is a group 4metal and the indenyl is unsubstituted or substituted by one or moresubstituents selected from the group consisting of a halogen atom, C₁ toC₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅ arylalkyl, and C₆ to C₂₅ alkylaryl,and wherein the metallocene has two leaving groups, X₁ and X₂, whichare, independently, hydrogen, halogen, hydride radicals, hydrocarbylradicals, substituted hydrocarbyl radicals, halocarbyl radicals,substituted halocarbyl radicals, silylcarbyl radicals, substitutedsilylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbylradicals; or both X are joined and bound to the metal atom to form ametallacycle ring containing from about 3 to about 20 carbon atoms; orboth together can be an olefin, diolefin or aryne ligand.
 30. Theprocess of claim 16, wherein the transition metal compound is ametallocene selected from the group consisting of a rac-dimethylsilylbis(indenyl) hafnocene, a rac-dimethylsilyl bis(indenyl) zirconocene, arac-dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnocene, arac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconocene, arac-dimethylsilyl bis(2-methyl-indenyl) hafnocene, a rac-dimethylsilylbis(2-methyl-indenyl) zirconocene, a rac-dimethylsilylbis(2-methyl-4-naphthylindenyl) hafnocene, a rac-dimethylsilylbis(2-methyl-4-naphthylindenyl) zirconocene, a rac-ethylenylbis(indenyl) hafnocene, rac-dimethylgermylbis(indenyl)hafnocene,rac-dimethylgermylbis(indenyl) zirconocene, and a rac-ethylenylbis(indenyl) zirconocene, and wherein the zirconocene or hafnocene havetwo leaving groups, X₁ and X₂, which are, independently, hydrogen,halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbylradicals, halocarbyl radicals, substituted halocarbyl radicals,silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbylradicals, or substituted germylcarbyl radicals; or both X are joined andbound to the metal atom to form a metallacycle ring containing fromabout 3 to about 20 carbon atoms; or both together can be an olefin,diolefin or aryne ligand.
 31. The process of claim 16, wherein thetransition metal compound and/or the activator are supported on a solidsupport.
 32. The process of claim 16, wherein the support comprisessilica or alumina.
 33. The process of claim 26, wherein A is nitrogen orphosphorus, n is 3, and the groups R are identical.
 34. The process ofclaim 26, wherein n is 3, and the groups R are all identically methyl,ethyl or propyl groups.
 35. The process of claim 26, wherein [R_(n)AH]⁺is trimethylammonium, trimethylphosphonium, triethylammonium,triethylphosphonium, tri(iso-propyl)ammonium,tri(iso-propyl)phosphonium, tri(n-propyl)ammonium, ortri(n-propyl)phosphonium.
 36. The process of claim 26, wherein[R_(n)AH]⁺ is an oxonium derivative of dimethyl ether, diethyl ether,tetrahydrofurane and dioxane.
 37. The process of claim 16, wherein thetransition metal compound is dimethylsilylbis(indenyl)hafnium dimethyl,rac-dimethylsilylbis(indenyl)zirconium dimethyl,rac-ethylenylbis(indenyl)zirconium dimethyl, orrac-ethylenylbis(indenyl)hafnium dimethyl and [R_(n)AH]⁺ istrimethylammonium.